JP2016207522A - Phototherapy apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phototherapy apparatus including organic electroluminescent element, which is excellent in durability of an electrode against folding, is suppressed in heat generation during emission and prevents a skin burn during therapy.SOLUTION: A phototherapy apparatus of the present invention includes, as a surface emitting light source, an organic electroluminescent element including a flexible base material and having an emission wavelength in a wavelength region of 400-2,000 nm. A transparent electrode constituting the organic electroluminescent element contains a metal material or a metal oxide material having an amorphous structure.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a phototherapy device, and more particularly to a phototherapy device including an organic electroluminescence element having low heat generation, flexibility, and improved bending resistance.

  Conventionally, it is known that treatment with light irradiation, so-called phototherapy, is effective for a specific disease. For example, treatment for pain relief such as stiff shoulders and low back pain and thin hair treatment is performed by irradiation with red light or infrared light. By expanding blood vessels with this infrared ray, for example, near-infrared light, the blood flow in the tissue is increased, the excitation of the sympathetic nervous system is suppressed, the cellular tissue is activated, and wound healing is promoted. It is well known that it acts on inflammatory cytokines and analgesics to produce anti-inflammatory and analgesic effects. In particular, it has been clarified that the near-infrared region in the vicinity of a wavelength of 800 to 900 nm with little absorption to water, hemoglobin, and melanin is excellent in living body permeability and suppresses inflammation and pain by an action mechanism different from the thermal effect. . On the other hand, it is said that treatment by irradiation with blue light or ultraviolet light is effective for the treatment of atopic dermatitis.

  Light is used for the treatment of various diseases in this way, and the method of using light irradiation alone for treatment is called phototherapy, and the treatment method that uses photochemotherapeutic agents together with light irradiation is photodynamic. It is called a therapy (PDT: Photo Dynamic Therapy). In this PDT, a photosensitive therapeutic agent known as a photochemotherapeutic agent is supplied to the treated area of the body from the outside or the inside. These therapies can be used to treat various skin and internal diseases.

  As a phototherapy device used for the above-described phototherapy, a plurality of light emitting means in which inorganic light emitting diodes (hereinafter abbreviated as LEDs) are arranged on a plane, and each of the light emitting means There has been proposed a phototherapy device that includes a control means for controlling the light emission amount and the light emission time, and performs treatment such as amelioration of inflammatory pain with near-infrared light (see, for example, Patent Document 1). According to the phototherapy device disclosed in Patent Document 1, the light intensity distribution and the temperature distribution on the treatment light irradiation surface are made uniform, and the treatment light is uniformly irradiated to the entire irradiation surface serving as a treatment site. It is said that the effect can be enhanced.

  However, an LED used as a light source has a rigid diffuser plate and the like, and is a light-emitting element with poor flexibility. For example, the curved surface structure of an affected area to be treated is irradiated with light uniformly. When trying to do so, it is necessary to arrange a large number of LEDs, the light emission control of a large number of LEDs becomes complicated, and the influence of heat generated by the LEDs themselves is also a problem.

  In response to the above problems, a phototherapy device using an organic light-emitting diode (hereinafter referred to as an organic electroluminescence element, an OLED, or an organic EL element) as a light source has been proposed. For example, a device for phototherapy is disclosed in which a mobile device used for therapeutic or cosmetic treatment is treated by light irradiation using an organic light-emitting diode as an organic light-emitting semiconductor in an area to be treated (for example, Patent Documents). 2). However, there is a problem that the applied electrode material is poor in flexibility.

  Further, a phototherapy device having an organic electroluminescence element that emits a therapeutic wavelength and a control module that controls light emission conditions of the organic electroluminescence element is disclosed (for example, see Patent Document 3). According to the method disclosed here, by selecting a plurality of OLEDs or controlling light emission with a control module, the light irradiation system can be controlled to irradiate light having a desired wavelength. .

  However, in these proposed OLEDs, a flexible material is used as the base material, but the electrodes, for example, the anode and the cathode, which are configured, are poor in flexibility, and the OLED corresponds to the shape of the affected part. When bending is repeated, the electrode, particularly the transparent electrode located on the light extraction side, is likely to be damaged, disconnected, or short-circuited, and the durability is insufficient. Moreover, since the light source part of the phototherapy device composed of a plurality of OLEDs emits heat with light emission and has an influence on the affected part due to heat, it is an obstacle to safe treatment and long-term treatment. Yes.

  It is also a phototherapy device using organic electroluminescence elements, using a flexible base material, for the purpose of monitoring a flexible conformal medical light source and blood properties (for example, the level of CO, oxygen, or bilirubin) Related diagnostic devices and phototherapy devices for the treatment of animals such as psoriasis and some forms of cancer have been disclosed (see, for example, US Pat.

  Patent Document 4 describes that the constituent electrode material is poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (PEDOT / PSS) or indium tin oxide (ITO) as a conductive polymer. However, the crystal structure of ITO is unknown. In addition, when PEDOT / PSS, which is a conductive polymer, is used as the electrode material, it is difficult to increase the area as an OLED, and there is a problem that heat is generated when the central portion of the light emitting surface is shined strongly. . In addition, when ITO having a highly crystalline structure is used, the electrode is easily damaged, disconnected or short-circuited. In addition, organic materials such as PEDOT / PSS generally have low heat conductivity, and thus have a problem that heat is easily stored and heat is easily generated.

JP 2009-055969 A JP 2005-520583 A Special table 2012-514498 gazette JP-T 2007-518467

  The present invention has been made in view of the above problems, and a solution to the problem is to provide an organic electroluminescence device that is excellent in durability of electrodes against bending, suppresses heat generation during light emission, and prevents burns during treatment. An optical therapy device is provided.

  As a result of intensive studies in view of the above problems, the present inventor has developed an organic electroluminescence device having a flexible base material, and the transparent electrode to be configured contains a metal material or a metal oxide material having an amorphous structure. It has been found that the phototherapy device provided can provide a phototherapy device including an organic electroluminescence element that has excellent durability of electrodes against bending, suppresses heat generation during light emission, and prevents burns during treatment. The present invention has been reached.

  That is, the said subject of this invention is solved by the following means.

1. A phototherapy device comprising an organic electroluminescence element as a surface light source on a flexible substrate,
The emission wavelength of the surface-emitting light source is in a wavelength range of 400 to 2000 nm,
The transparent electrode which comprises the said organic electroluminescent element contains the metal oxide material which has a metal material or an amorphous structure, and has flexibility, The phototherapy apparatus characterized by the above-mentioned.

  2. 2. The phototherapy device according to claim 1, wherein the metal oxide material is an amorphous indium oxide compound, an amorphous zinc oxide compound, or an amorphous tin oxide compound.

  3. 3. The phototherapy device according to item 1 or 2, wherein the metal oxide material is amorphous indium tin oxide, amorphous indium zinc oxide, or amorphous zinc oxide.

  4). 2. The phototherapy device according to item 1, wherein the metal material is silver or aluminum.

  5. The transparent electrode constituting the organic electroluminescence element has a metal electrode layer mainly composed of silver and a base layer containing a substance having an interaction with silver at a position adjacent to the metal electrode layer. Item 5. The phototherapy device according to Item 1 or 4, wherein the device is for phototherapy.

  6). The phototherapy device according to any one of items 1 to 5, wherein a photochemotherapeutic agent is used together with the organic electroluminescence element.

  By the above means of the present invention, it is possible to provide a phototherapy device comprising an organic electroluminescence element which has excellent electrode durability against bending, suppresses heat generation during light emission, and prevents burns during treatment.

  It is presumed that the above problem can be solved by the configuration defined in the present invention for the following reason.

  Generally, there is a correlation between heat conduction and electron conduction, and the easier the current flows, the easier the heat flows. Therefore, the order of the ease of heat flow due to electrons, in other words, the ease of heat dissipation, is in the order of metal material> amorphous metal oxide >> conductive polymer.

  Therefore, when a transparent electrode is formed of a conductive polymer alone, the heat conductivity is low, so that heat is easily generated, and the organic electroluminescence element at the time of phototherapy becomes high temperature. In contrast, in a metal material or amorphous metal oxide with many free electrons, heat generated by light emission is easily diffused, and a low temperature environment can be maintained during phototherapy.

  In addition, metal materials, amorphous metal oxide materials, and polymer materials are used as materials used in electronic devices that require flexibility.

  From the above two items, by containing a metal material or a metal oxide material having an amorphous structure in the transparent electrode, it is possible to suppress burns due to heat generation and to prevent breakage, disconnection, or short circuit.

  From these things, the transparent electrode which comprises an organic electroluminescent element contains a metal oxide material which has a metal material or an amorphous structure, has shape compatibility (flexibility), is excellent in bending resistance, In addition, it was possible to realize a phototherapeutic device including an organic electroluminescence element having a high luminance with a small calorific value when emitting light.

Schematic which shows an example of the phototherapy method using the apparatus for phototherapy provided with the flexible organic EL element Schematic sectional view showing an example (embodiment 1) of the overall configuration of an organic EL element having one organic functional layer unit Schematic sectional drawing which shows an example of the specific structure of the light emission unit of the organic EL element of Embodiment 1. Schematic sectional view showing another example (embodiment 2) of the configuration of the organic EL element having one organic functional layer unit Schematic sectional view showing an example (embodiment 3) of a configuration of an organic EL element having two organic functional layer units Schematic sectional view showing an example (embodiment 4) of another configuration of an organic EL element having two organic functional layer units Schematic sectional view showing an example (embodiment 5) of another configuration of an organic EL element having two organic functional layer units Schematic sectional view showing an example (embodiment 6) of a configuration of an organic EL element having three organic functional layer units

  The phototherapy device of the present invention is a phototherapy device comprising an organic electroluminescence element as a surface light source on a flexible substrate, and the light emission wavelength of the surface light source is in a wavelength range of 400 to 2000 nm. The transparent electrode constituting the organic electroluminescence element contains a metal material or a metal oxide material having an amorphous structure, has flexibility, has excellent electrode durability against bending, and generates heat during light emission. It is possible to realize a phototherapy device including an organic electroluminescence element that suppresses and prevents burns during treatment. This feature is a technical feature common to the inventions according to claims 1 to 6.

  As an embodiment of the present invention, an amorphous indium oxide-based compound, an amorphous zinc oxide-based compound, or a metal oxide material having an amorphous structure that constitutes a transparent electrode, from the viewpoint of more manifesting the intended effect of the present invention. More specifically, it is an amorphous tin oxide compound, more specifically, amorphous indium tin oxide (hereinafter also referred to as a-ITO), amorphous indium oxide / zinc (hereinafter also referred to as a-IZO), or amorphous oxidation. Zinc (hereinafter also referred to as a-ZnO) can provide excellent conductivity as an electrode, can form a highly flexible electrode, and has higher bending resistance. A luminescence element can be obtained, corresponding to the shape of the affected area, and stable phototherapy Effect can be obtained.

  Moreover, as a metal material which comprises a transparent electrode, it is silver or aluminum, and can form the electrode which comprised the same excellent electrode characteristic and flexibility, and the organic electroluminescent element excellent in bending resistance It is possible to obtain a stable phototherapy effect corresponding to the shape of the affected area.

  In addition, the transparent electrode has a structure in which a metal electrode layer mainly composed of silver and a base layer containing a substance that interacts with silver are formed at positions adjacent to the metal electrode layer. When forming a silver thin film electrode layer, it is possible to prevent the formation of sea-island aggregates (motors) of silver atoms, resulting in the formation of a silver thin film electrode with high light transmission and excellent uniformity. be able to.

  In the phototherapy device of the present invention, it is preferable to use a photochemotherapeutic agent together with phototherapy using an organic electroluminescence element from the viewpoint of further enhancing the phototherapy effect.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in this invention is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

《Phototherapy device》
The phototherapy device of the present invention comprises an organic electroluminescent element as a surface-emitting light source on a flexible substrate, the emission wavelength of the surface-emitting light source is in a wavelength range of 400 to 2000 nm, and the organic electroluminescent element is The transparent electrode to be formed contains a metal material or a metal oxide material having an amorphous structure, and has flexibility.

  The transparent electrode as used in the field of this invention means that the transmittance | permeability of the light light-emitted by the light emitting layer is 50% or more, Preferably it is 70% or more, Most preferably, it is 85% or more. Specifically, the transparent electrode is an electrode arranged at least on the light extraction side, and when light extraction is performed from the anode side, the anode and the intermediate electrode correspond to the transparent electrode in the present invention. In many cases, an electrode located farthest from the light extraction side, for example, a cathode, is often composed of a light-impermeable reflective electrode.

  FIG. 1 is a schematic diagram illustrating an example of a state where a phototherapy device including an organic EL element having flexibility is applied to an affected area of a curved surface.

  In FIG. 1, the organic EL element (OLED) according to the present invention includes a light emitting unit (12) sandwiched between a pair of electrodes on a flexible substrate (1), and a sealing adhesive layer (13) on the light emitting unit (12). ) And a flexible sealing substrate (14), and the light emitting layer unit is connected to a light emission control means (not shown) for controlling the light emission amount and the light emission time.

  Since the organic EL element (OLED) according to the present invention is composed of a flexible member as shown in FIG. 1, the shape of the light emitting surface can be freely set, and the affected part (2) having a curved surface It is possible to stably emit light (L) for phototherapy, which enables stable phototherapy.

  In the following description, a configuration in which an organic functional layer unit including a light emitting layer sandwiched between a pair of electrodes and a flexible sealing member is provided on at least a flexible substrate is referred to as an “organic EL element (OLED)”, an anode, The structure composed of the light emitting layer, the organic functional layer group, and the cathode is referred to as “light emitting unit (12)”, and the structure composed of the light emitting layer and the organic functional layer group is referred to as “organic functional layer unit (4)”.

<< Organic EL element >>
[1. Basic Configuration of Organic EL Element: Embodiment 1]
FIG. 2 is a schematic cross-sectional view showing an example (embodiment 1) of the entire configuration of an organic EL element having one organic functional layer unit.

  In FIG. 2, the organic EL element (OLED) according to the present invention includes a first electrode (3, anode) constituting a pair of electrodes on the flexible substrate (1), and an organic functional layer group 1 thereon. (22) It has the organic functional layer unit (4) comprised by the light emitting layer (23) and the organic functional layer group 2 (24). In FIG. 2, only one organic functional layer unit (4) is shown for convenience, but a structure in which two or more organic functional layer units (4) are stacked may be used as necessary. A second electrode (6, cathode) is formed on the organic functional layer unit (4), and the first electrode (3) to the second electrode (6) constitute a light emitting unit (12). . An upper part of the second electrode (6) is provided with a sealing adhesive layer (13) and a flexible sealing substrate (14) so as to cover at least the organic functional layer unit (4). (OLED) is formed.

  In the organic EL element (OLED) shown in FIG. 2, the anode that is the first electrode (3) is formed of a transparent electrode, so that the emitted light (L) emitted from the light emitting point (h) of the light emitting layer (23). ) Is taken out from the first electrode (3) side which is a transparent electrode. At this time, the cathode as the second electrode (6) becomes a light-impermeable reflective electrode as shown in the figure.

  The organic EL element (OLED) applied to the phototherapy device of the present invention is characterized in that the emission wavelength is in the range of 400 to 2000 nm. By having such a wide light emission wavelength range, light having a wavelength suitable for phototherapy can be selected as needed. Such control of the emission wavelength can be realized by the type of the luminescent compound used in the luminescent layer of the organic EL element, the combination of two or more luminescent compounds, or the formation of a plurality of luminescent layers.

  Moreover, when the organic EL element which concerns on this invention is the structure which laminates | stacks two or more organic functional layer units, each organic functional layer unit sets a different light emission maximum wavelength (henceforth light emission peak wavelength). It is preferable to have a configuration that can select and irradiate light having an appropriate wavelength depending on the treatment target. In addition, by having two or more organic functional layer units each having the same emission peak wavelength, it is possible to efficiently irradiate the affected area as a treatment target with high-intensity light without generating heat. This is preferable.

  FIG. 3 is a schematic cross-sectional view showing an example of a specific configuration of the organic EL element (OLED) according to Embodiment 1 described in FIG.

  In the organic EL element (OLED) having the configuration shown in FIG. 3, an anode (3) is disposed as a transparent electrode on a flexible substrate (1), and a hole injection layer (HIL) and a hole transport layer are formed thereon. The first organic functional layer group (22) is formed by stacking (HTL). A light emitting layer (23) is provided on the first organic functional layer group (22). On this light emitting layer (23), the 2nd organic functional layer group (24) which laminated | stacked the electron carrying layer (ETL) and the electron injection layer (EIL) is formed, and the cathode (6) is used as a reflective electrode in the uppermost layer. It is provided and constitutes the light emitting unit (12). When the final organic EL element is configured, as shown in FIG. 2, a structure in which the organic EL element is sealed with a sealing member is employed, but the description thereof is omitted in FIG.

  In the configuration shown in FIG. 3, by applying a voltage (V1) between the transparent anode (3) and the cathode (6), light is emitted at the light emitting layer or the light emitting layer interface, and the anode (3 The emitted light (L) is emitted from the) side. At this time, as shown in FIG. 2, the cathode as the second electrode (6) reflects the incident emitted light (L) on the surface of the cathode, which is a light-impermeable reflection electrode, and passes through the transparent electrode. Radiates to a certain anode (3) side.

  In general, the light emitting layer of the organic EL element is formed of a light emitting dopant (for example, a phosphorescent compound or a fluorescent compound) described later in detail and a host compound.

[2. Typical configuration of organic EL element]
As described with reference to FIGS. 2 and 3, the organic EL element (OLED) according to the present invention, from below, on the flexible substrate (1), the anode (3) as the first electrode, and then, for example, the positive electrode Organic functional layer group 1 (22) composed of a hole injection layer, a hole transport layer, and the like, and light emitting layer (23), for example, organic functional layer group 2 (24) composed of an electron transport layer, an electron injection layer, and the like Are stacked to have an organic functional layer unit (4) constituting a light emitting region. And the cathode (6) which is a 2nd electrode, the contact bonding layer (13), and the sealing base material (14) are provided in the upper part.

  The configuration example of the organic EL element applicable to the phototherapy device of the present invention is not particularly limited as long as the conditions specified in the present invention are satisfied, and configurations (1) to (6) shown below are representative examples. Can be mentioned. However, the present invention is not limited to these exemplified configurations.

  Below, the typical example of a structure of the organic EL element applicable to this invention is shown.

(1) Flexible substrate / anode / organic functional layer unit [organic functional layer group 1 / light emitting layer / organic functional layer group 2] / cathode / sealing member (see embodiment 1, FIG. 2 and FIG. 3)
(2) Flexible substrate / underlayer / anode (for example, silver thin film electrode) / organic functional layer unit [organic functional layer group 1 / light emitting layer / organic functional layer group 2] / cathode / sealing member (Embodiment 2, (See Figure 4)
(3) Flexible substrate / anode / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / intermediate electrode / organic functional layer unit 2 [organic functional layer group 1B / light emitting layer B / Organic functional layer group 2B] / cathode / sealing member (embodiment 3, see FIG. 5)
(4) Flexible substrate / underlayer / anode (for example, silver thin film electrode) / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / intermediate electrode / organic functional layer unit 2 [Organic functional layer group 1B / light emitting layer B / organic functional layer group 2B] / cathode / sealing member (see embodiment 4, FIG. 6)
(5) Flexible substrate / Anode / Organic functional layer unit 1 [Organic functional layer group 1A / Light emitting layer A / Organic functional layer group 2A] / Underlayer / Intermediate electrode (for example, silver thin film electrode) / Organic functional layer unit 2 [Organic Functional Layer Group 1B / Light-Emitting Layer B / Organic Functional Layer Group 2B] / Cathode / Sealing Member (Embodiment 5, see FIG. 7)
(6) Flexible substrate / anode / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / underlayer 1 / intermediate electrode 1 (for example, silver thin film electrode) / organic functional layer Unit 2 [organic functional layer group 1B / light emitting layer B / organic functional layer group 2B] / underlayer 2 / intermediate electrode 2 (for example, silver thin film electrode) / organic functional layer unit 3 [organic functional layer group 1C / light emitting layer C / Organic functional layer group 2C] / Cathode / Sealing member (Embodiment 6, see FIG. 8)
Further, in the case of forming a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers. The intermediate layer may be a charge generation layer or a multi-photon unit configuration.

  In the configurations (1) to (6) described above, when light extraction is performed from the anode side, the anode and the intermediate electrode correspond to the transparent electrode according to the present invention, and the cathode serves as the reflective electrode.

  Regarding the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A, JP JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A, JP 2013-235994 A, JP 2013-243234 A, JP 2013-243236 A, JP 2013-2013 A. JP 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-014933 Gazette, JP, 2014-017494, A It can be mentioned configurations described in.

  Specific examples of the organic EL element in which two or more organic functional layer units are laminated include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734, US Pat. No. 6,337,492, JP-A 2006-228712, JP-A 2006-24791, JP-A 2006-49393, JP-A 2006-49394. Publication, JP 2006-49396, JP 2011-96679, JP 2005-340187, JP 47114424, JP 34966681, JP 3884564, JP 431169 JP, 2010-192719, JP, 20 No. 9-076929, JP 2008-078414 A, JP 2007-059848 A, JP 2003-272860 A, JP 2003-045676 A, International Publication No. 2005/009087, International Publication No. 2005. / 094130 etc., the element structure, a constituent material, etc. are mentioned, However, This invention is not limited to these.

[3. Components of organic EL element]
[3.1: Electrode configuration]
First, the details of the electrode material, which is a structural feature of the present invention, will be described.

  In the organic EL device according to the present invention, the transparent electrode constituting the organic EL device contains a metal material or a metal oxide material having an amorphous structure, and corresponds to the form of the affected area during phototherapy, Even when bending or the like is performed, it is possible to suppress the occurrence of electrode breakage, disconnection, and short circuit due to high flexibility.

  The “transparent” of the transparent electrode in the present invention means that the transmittance of light emitted from the light emitting layer is 50% or more, preferably 70% or more, particularly preferably 85% or more. .

  For example, in the case where emitted light is extracted from the anode side, the transparent electrode according to the present invention corresponds to the anode and the intermediate electrode, and the cathode located on the non-light emitting surface side functions as a reflective electrode. Not applicable to electrodes. For example, when an electrode having a thickness of 100 nm or more is formed of aluminum as the cathode, it becomes a light-impermeable reflective electrode.

(Outline of electrode)
<anode>
As the anode according to the present invention, a metal having a large work function (4 eV or more) or an alloy containing a metal as a main component or a metal oxide material having an amorphous structure is used as a main component.

  In addition, the anode may be formed by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering, and a desired shape pattern may be formed by a photolithography method, or the pattern accuracy is not required so much (about 100 μm or more) ) May form a pattern through a mask having a desired shape during vapor deposition or sputtering of the electrode material. In addition, in the case of using a metal material or a metal oxide material having an amorphous structure together with an applicable substance such as an organic conductive compound, a wet film formation method such as a printing method or a coating method can be used. In the case of extracting light emission from the anode, it is necessary to make the transmittance of the emitted light larger than 50% as the anode, and preferably 70% or more. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually in the range of 10 to 500 nm, preferably in the range of 10 to 200 nm.

<Intermediate electrode>
The organic EL device according to the present invention may have a structure in which two or more organic functional layer units each composed of an organic functional layer group and a light emitting layer are laminated between an anode and a cathode. In order to obtain electrical connection between the organic functional layer units, it is preferable to take a structure in which the organic functional layer units are separated by an intermediate electrode having independent connection terminals.

  For the intermediate electrode, the above-described anode forming material can be used in the same manner.

<cathode>
The cathode according to the present invention is an electrode film that functions to supply holes to the organic functional layer group and the light emitting layer, and is mainly a metal material such as aluminum, and the film thickness is usually 100 nm to 5 μm, preferably Since it is selected in the range of 100 to 200 nm, it often does not have optical transparency.

  The cathode can be produced by forming a thin film of electrode material by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less. A transparent or semi-transparent cathode can be produced by forming a metal such as aluminum with a film thickness of 1 to 20 nm on the cathode and then forming a conductive transparent material applicable to the anode thereon. By applying this, an organic EL element in which both the anode and the cathode are transparent can be produced.

  Next, a metal material applied to each electrode and a metal oxide material having an amorphous structure will be described.

(3.1.1: Metal material)
As an electrode material applied to the formation of an electrode, from the viewpoint of imparting flexibility, which is an object effect of the present invention, an excellent conductivity can be obtained, and a thin film having excellent ductility and malleability and high flexibility can be obtained. Metal materials that can be formed are preferred.

  The metal material may be a single metal or an alloy. Examples of such metal materials include metals such as silver, gold, and aluminum. Examples of the metal-based alloy include sodium-potassium alloy, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, silver-copper (Ag-Cu), silver-palladium ( Ag-Pd), silver-palladium-copper (Ag-Pd-Cu), silver-indium (Ag-In), and the like.

  In the present invention, the metal material is preferably silver or aluminum, and more preferably silver.

  The thickness of the transparent electrode made of a metal material is preferably in the range of 2 to 40 nm, more preferably in the range of 4 to 20 nm. A thickness of 20 nm or less is preferable because the absorption component and reflection component of the transparent anode can be kept low and high light transmittance can be maintained. When the thickness of the electrode made of a metal material exceeds 40 nm, the light transmittance is lowered, and a reflective electrode applied to the cathode side is obtained.

<Silver electrode>
In the present invention, in particular, among the constituent materials constituting the anode that requires transparency, the anode constituting the organic EL element according to the present invention is composed mainly of silver and has a thickness of 2 to 40 nm. The transparent anode is preferably in the range of 5 to 20 nm, more preferably in the range of 4 to 20 nm. A thickness of 40 nm or less is preferable because the absorption component and reflection component of the transparent anode can be kept low and high light transmittance can be maintained.

  In the present invention, the layer composed mainly of silver means that the silver content in the transparent anode is 60% by mass or more, preferably the silver content is 80% by mass or more, More preferably, the silver content is 90% by mass or more, and particularly preferably the silver content is 98% by mass or more. Further, “transparent” in the transparent anode according to the present invention means that the transmittance of light emitted from the light emitting layer is 50% or more.

  The transparent anode may have a configuration in which a layer composed mainly of silver is divided into a plurality of layers as necessary.

<Underlayer>
In the present invention, in the case where the electrode is composed mainly of silver, it is preferable to provide a base layer below the silver electrode from the viewpoint of improving the uniformity of the silver electrode to be formed. Although there is no restriction | limiting in particular as a base layer, It is preferable that it is a layer containing the organic compound which has a nitrogen atom or a sulfur atom, and the method of forming a transparent silver electrode on the said base layer is a preferable aspect.

  The underlayer may be a layer containing a compound that interacts with silver, and the compound may be composed of a Lewis base, that is, a compound containing an atom having an unshared electron pair. preferable. Examples of such a compound having a Lewis base include nitrogen-containing compounds and sulfur-containing compounds. The nitrogen-containing compound may be a compound containing a nitrogen atom (N), but is particularly an organic compound containing a nitrogen atom having an unshared electron pair, and is preferably the following compound. That is, the nitrogen-containing compound constituting the underlayer is a non-shared electron pair of nitrogen atoms that are stably bonded to silver, which is the main material constituting the metal electrode layer 11, among nitrogen atoms contained in the compound [ In the case of [effective unshared electron pair], the content ratio of the [effective unshared electron pair] is preferably within a predetermined range.

  Here, “effective unshared electron pair” means an unshared electron pair that is not involved in aromaticity and is not coordinated to a metal among the unshared electron pairs of the nitrogen atom contained in the compound. And The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel's rule”. The condition is that the number is “4n + 2” (n = 0 or a natural number).

  For details of the foundation layer according to the present invention, for example, the contents described in JP-A-2015-046364, JP-A-2015-060728, and the like can be referred to.

  The constituent material of the transparent electrode according to the present invention is particularly preferably a structure in which a thin film silver layer is formed on the above-described underlayer, and further, silver having the above-mentioned underlayer on the anode on the light extraction side. It is a preferable configuration to apply a thin film electrode.

<Grid electrode>
As an electrode formed of the metal material according to the present invention, in addition to a uniform thin film electrode, it can be applied in the form of a grid electrode formed of fine wires.

  The grid electrode is composed of conductive fine metal wires. The shape of the grid electrode is not limited to a lattice shape, and various shapes of grids such as a stripe shape, a honeycomb structure shape, and a mesh shape can be used. From the viewpoint of obtaining uniform conductivity regardless of the position, a grid having a periodic shape located on the entire surface of the organic EL element is preferable.

  The line width of the fine metal wire constituting the grid electrode is preferably in the range of 10 to 200 μm, and the height of the fine wire is preferably in the range of 0.1 to 10.0 μm.

  The aperture ratio of the grid electrode is preferably 80% or more from the viewpoint of improving transparency. The aperture ratio is the ratio of the area occupied by the region where the fine metal wires forming the grid electrode are not arranged in the light emitting area of the organic EL element. For example, the aperture ratio of a grid electrode in which fine metal wires having a line width of 100 μm and a line interval of 1 mm are formed in a stripe shape or a lattice shape is about 90%.

  Examples of the conductive metal material that can be used for the fine metal wires constituting the grid electrode include gold, silver, copper, iron, cobalt, nickel, chromium, and alloys thereof. From the viewpoint of low resistance, silver or copper is preferable, and silver is more preferable.

  For grid electrodes, a coating solution containing metal nanoparticles using metal materials, metal complexes, etc. is desired by letterpress printing, intaglio printing, stencil printing, screen printing, ink jet, ink jet parallel line drawing, etc. It can form by apply | coating to the shape of. The ink jet parallel line drawing method uses a coffee stain phenomenon in which when the coating liquid is applied in a line shape, the coating liquid flows from the center to the end of the line and solidification of the end proceeds. This is a method of forming two parallel lines from a line.

  After the grid electrode is formed, a conductive polymer layer can be formed on the upper portion of the grid electrode as long as the object effects of the present invention are not impaired. As the conductive polymer, a π-conjugated conductive polymer containing a polyanion can be used.

  Examples of π-conjugated conductive polymers that can be used include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes. , Polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds and the like. Of these, polythiophenes or polyanilines are preferable and polyethylenedioxythiophene is more preferable from the viewpoint of improving conductivity, transparency, stability, and the like.

  Also, the grid electrode surface can be plated.

<Metal nanomaterial-containing electrode>
The metal nanomaterial that can be used to form the metal nanomaterial-containing electrode is a metal material having a nanoscale size, and is also called a nanotube, nanowire, nanofiber, or the like depending on the shape. Examples of the metal include silver (Ag), aluminum (Al), copper (Cu), gold (Au), tungsten (W), molybdenum (Mo), and alloys thereof. Among these, silver is preferable because it has low resistance, high conductivity, and can be easily processed into a desired shape.

  The metal nanomaterial-containing electrode can be formed by preparing and applying a coating solution containing the metal nanomaterial. In the coating solution for forming the metal nanomaterial-containing electrode, for example, polyvinylpyrrolidone or the like can be used as a binder for holding the metal nanomaterial.

  In addition, after the metal nanomaterial-containing electrode is formed, a conductive polymer layer can be formed on the upper portion within a range that does not impair the object effect of the present invention. As the conductive polymer, a π-conjugated conductive polymer containing a polyanion can be used.

  Examples of π-conjugated conductive polymers that can be used include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes. , Polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds and the like. Of these, polythiophenes or polyanilines are preferable and polyethylenedioxythiophene is more preferable from the viewpoint of improving conductivity, transparency, stability, and the like.

(3.1.2: Metal oxide material having an amorphous structure)
In forming the transparent electrode according to the present invention, one of the features is that a metal oxide material having an amorphous structure is used.

  By using a metal oxide material having an amorphous amorphous structure instead of a crystalline material for forming each electrode according to the present invention, flexibility can be imparted to the electrode, and the form of the affected part during phototherapy Even if the bending operation is performed in accordance with the above, it is possible to suppress the destruction / disconnection of the electrode and the occurrence of a short circuit.

  The metal oxide material having an amorphous structure according to the present invention is not particularly limited as long as it is an amorphous metal oxide, but is preferably an amorphous indium oxide compound, an amorphous zinc oxide compound, or amorphous tin oxide. It is a system compound, More preferably, it is amorphous indium oxide tin (a-ITO), amorphous indium oxide zinc (a-IZO), or amorphous zinc oxide (a-ZnO).

  The term “amorphous” as used in the present invention refers to measured X-ray diffraction with little three-dimensional regularity as atoms or molecules constituting a solid when XRD analysis (X-ray diffraction method) of the formed thin film is performed. In the spectrum, only a halo pattern is observed, and it is defined as a substance that does not show a specific diffraction line peak indicating crystallinity.

  Examples of the XRD measurement apparatus that can be used in the above measurement include X-ray diffractometers XRD-7000 and XRD-6100 manufactured by Shimadzu Corporation, X-ray diffractometers manufactured by Rigaku Corporation (XRD measurement apparatuses RINT2200, RINT-TTR2, and SWRD). Etc.).

  Examples of the metal oxide having an amorphous structure that can be suitably used for forming the electrode according to the present invention include amorphous indium tin oxide (a-ITO), amorphous indium oxide zinc (a-IZO), and amorphous oxide. Examples thereof include indium / gallium / zinc (a-IGZO) and amorphous zinc oxide (a-ZnO). Amorphous zinc oxide / tin (a-ZSnO) can also be used.

  In an electrode composed of a metal oxide material having an amorphous structure according to the present invention, a dielectric material or an oxide semiconductor material is used as the other metal oxide within a range in which amorphousness (amorphous) can be maintained. Can do.

  The amorphous layer (5A) can be formed by vapor deposition or sputtering. Deposition methods applicable to the present invention include resistance heating vapor deposition, electron beam vapor deposition, ion plating, and ion beam vapor deposition. As the vapor deposition apparatus, for example, a BMC-800T vapor deposition machine manufactured by SYNCHRON, Inc. can be used.

  The sputtering method according to the present invention includes bipolar sputtering method, magnetron sputtering method, DC sputtering method, DC pulse sputtering method, RF (radio frequency) sputtering method, dual magnetron sputtering method, reactive sputtering method, ion beam sputtering method, bias A known sputtering method such as a sputtering method or a counter target sputtering method can be used as appropriate. In addition, when a substance that can be applied such as an organic conductive compound, for example, the above-described conductive polymer is used in combination, a wet film formation method such as a printing method or a coating method can be used.

(3.1.3: Heat generation and heat dissipation during light emission by electrode forming material type)
Generally, there is a correlation between heat conduction and electron conduction, and the easier the current flows, the easier the heat flows. Therefore, the order of the ease of heat flow due to electrons (ease of heat dissipation) is metal material> amorphous metal oxide >> conductive polymer. When an electrode is formed of a conductive polymer alone, the heat conductivity is low, so that heat is easily generated and the temperature becomes high during phototherapy. On the other hand, in a metal material or amorphous metal oxide with many free electrons, heat generated by light emission is easily scattered, and a low temperature environment can be maintained during phototherapy.

  Next, details of each constituent material of the organic EL element excluding the above-described electrodes will be described.

[3.2: Flexible base material]
There is no restriction | limiting in particular as a flexible base material (1) applicable to an organic EL element (OLED), For example, types, such as glass and a plastic, can be mentioned. The term “flexible” as used in the present invention means that the substrate is cracked or chipped by visual inspection after being repeatedly wound and released 10 times around a rod made of ABS resin (acrylonitrile-butadiene-styrene copolymer resin) having a diameter of 5 mm. A characteristic that is not damaged.

  In the present invention, the flexible base material (1) arranged on the light emitting surface side (light extraction surface) irradiates the affected area to be treated with the light irradiated by the organic EL element, and therefore, in the wavelength range of 400 to 2000 nm. It is necessary to have optical transparency. The light transmittance in the present invention means that the flexible substrate (1) has a transmittance in the wavelength region of 400 to 2000 nm of 50% or more, preferably 70% or more, more preferably 80% or more. Particularly preferably, it is 90% or more.

  That is, in this invention, as shown in each figure, in the structure which takes out light (L) from the flexible base material (1) side, a flexible base material (1) needs to be a transparent material, and is used preferably. Examples of the transparent flexible substrate (1) include glass, quartz and resin substrates. More preferably, it is a resin base material from the viewpoint of safety, which can impart flexibility to the organic EL element.

  Examples of the resin base material applicable to the present invention include polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose triacetate (abbreviation: TAC). ), Cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate and their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene , Polycarbonate (abbreviation: PC), norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone ( Name: PES), polyphenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic and polyarylates, Arton (trade name, manufactured by JSR) and Appel (product) Name, manufactured by Mitsui Chemicals, Inc.) and the like.

  Among these resin substrates, films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC) are flexible in terms of cost and availability. It is preferably used as a resin base material.

  In addition, the flexible substrate may be subjected to a surface activation treatment as necessary, or may be provided with each functional layer such as a base layer, a gas barrier layer, and a hard coat layer.

  Examples of the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

  The gas barrier layer can be formed by a conventionally known method. For example, a method of forming by modifying a film of a silicon-containing polymer having a bond of silicon and oxygen (Si-O), silicon and nitrogen (Si-N), etc. in a repetitive structure, herhydropolysilazane, etc. And a method of forming by a plasma CVD method or the like.

  Examples of the material for the underlayer and the hard coat layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer, and the like. Of these, ultraviolet curable resins can be preferably used. The underlayer may be a single layer, but the adhesiveness is further improved when it has a multilayer structure.

  The thickness of the resin substrate is preferably a thin resin substrate in the range of 10 to 500 μm, more preferably in the range of 30 to 400 μm, and particularly preferably in the range of 50 to 300 μm. Is within. If the thickness is 10 μm, the organic EL element can be stably held, and if the thickness is 500 μm or less, the thermal energy generated during phototherapy can be efficiently diffused, and the patient Can adhere to the skin even while wearing clothes.

  Moreover, the thin plate flexible glass applicable as the flexible base material (1) according to the present invention is a glass plate that is thin enough to be bent. The thickness of the thin flexible glass can be appropriately set within the range where the thin flexible glass exhibits flexibility.

  Examples of the thin flexible glass include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. As thickness of thin plate flexible glass, it is the range of 10-500 micrometers, for example, Preferably it is the range of 50-300 micrometers.

[3.3: Light-emitting layer]
In the light emitting layer (23) constituting the organic EL element (OLED), a phosphorescent light emitting compound or a fluorescent compound can be used as the light emitting material. In the present invention, in particular, a phosphorescent light emitting compound is used as the light emitting material. The contained structure is preferable.

  This light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

  Such a light emitting layer is not particularly limited in its configuration as long as the contained light emitting material satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer between the light emitting layers.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between light emitting layers.

  For the light emitting layer as described above, a light emitting material and a host compound to be described later may be used by publicly known methods such as a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir-Blodget, Langmuir Broadgett method), and an ink jet method. Can be formed.

  The light-emitting layer may be a mixture of a plurality of light-emitting materials, or a phosphorescent light-emitting material and a fluorescent light-emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light-emitting layer. The structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound), and emits light from the light-emitting material.

(3.3.1: Host compound)
As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As the host compound, a known host compound may be used alone, or a plurality of types of host compounds may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescent device can be improved. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used in the light emitting layer may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). )

  Examples of the host compound applicable to the present invention include, for example, JP-A Nos. 2001-257076, 2001-357777, 2002-8860, 2002-43056, 2002-105445, 2002-352957, 2002-231453, 2002-234888, 2002-260861, 2002-305083, US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0030202, International Publication No. 2001/039234, International Publication No. 2008/056746, International Publication No. 2005/089025, International Publication No. 2007/063754, International Publication No. 2005/030900, International Publication 2009 No. 086028, WO 2012/023947, can be mentioned JP 2007-254297, JP-European compounds described in Japanese Patent No. 2034538 Pat like.

(3.3.2: Luminescent material)
As the light-emitting material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material, or a phosphorescent dopant) and a fluorescent compound (both a fluorescent compound or a fluorescent material) are used. In particular, it is preferable to use a phosphorescent compound from the viewpoint of obtaining high luminous efficiency.

<Phosphorescent compound>
A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. More preferred are iridium compounds, more preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds) or rare earth complexes, and most preferred are iridium compounds.

  In the present invention, at least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.

  Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents.

  Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. Examples thereof include compounds described in US Patent No. 0202194, US Patent Application Publication No. 2007/0087321, US Patent Application Publication No. 2005/0244673, and the like.

  Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2009/000673, US Pat. No. 7,332,232, US Patent Application Publication No. 2009/0039776, US Pat. No. 6,687,266, US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,396,598, US Patent Application Publication No. 2003/0138667, US Pat. No. 7090928 And the like.

  Also, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2006/056418, International Publication No. 2005/123873, International Publication No. 2005/123873, International Publication No. 2006/082742, US Patent Application Publication No. 2005/0260441. U.S. Pat. No. 7,534,505, U.S. Patent Application Publication No. 2007/0190359, U.S. Pat. No. 7,338,722, U.S. Pat. No. 7,279,704, U.S. Patent Application Publication No. 2006/103874, etc. Mention may also be made of the compounds described.

  Furthermore, International Publication No. 2005/076380, International Publication No. 2008/140115, International Publication No. 2011/134013, International Publication No. 2010/086089, International Publication No. 2012/020327, International Publication No. 2011/051404. Further, compounds described in International Publication No. 2011/073149, JP2009-114086, JP2003-81988, JP2002-363552, and the like can also be mentioned.

  In the present invention, preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, or a metal-sulfur bond is preferable.

  The phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, 4, 695-709 (2004), and methods disclosed in the references described in these documents. Can be synthesized.

<Fluorescent compound>
Fluorescent compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes. And dyes, polythiophene dyes, and rare earth complex phosphors.

[3.4: Organic functional layer]
Next, each layer constituting the organic functional layer unit will be described in the order of a charge injection layer, a hole transport layer, an electron transport layer, and a blocking layer.

(3.4.1: Charge injection layer)
The charge injection layer is a layer provided between the electrode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998, NT. The details are described in Chapter 2, “Electrode Material” (pages 123 to 166) of the second edition of “S. Co., Ltd.”, and there are a hole injection layer (HIL) and an electron injection layer (EIL).

  In general, the charge injection layer is present between the anode and the light emitting layer or the hole transport layer in the case of a hole injection layer, and between the cathode and the light emitting layer or the electron transport layer in the case of an electron injection layer. However, the present invention is characterized in that the charge injection layer is disposed adjacent to the transparent electrode. When used in an intermediate electrode, it is sufficient that at least one of the adjacent electron injection layer and hole injection layer satisfies the requirements of the present invention.

  The hole injection layer is a layer disposed adjacent to the anode, which is a transparent electrode, in order to lower the driving voltage and improve the luminance of light emission. “The organic EL element and its industrialization front line (November 30, 1998 (Issued by TS Co., Ltd.) ”, Chapter 2“ Electrode Materials ”(pages 123 to 166) in the second volume.

  The details of the hole injection layer are described in JP-A-9-45479, 9-260062, 8-28869, etc., and these compounds can be used for the hole injection layer. it can.

  In addition, hexaazatriphenylene derivatives such as those described in JP-A-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.

  The electron injection layer is a layer provided between the cathode and the light emitting layer for lowering the driving voltage and improving the light emission luminance. When the cathode is composed of the transparent electrode according to the present invention, Chapter 2 “Electrode materials” (pages 123-166) of the second edition of “Organic EL elements and their forefront of industrialization” (published on November 30, 1998 by NTT) ) Is described in detail.

  The details of the electron injection layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. It can be preferably used. The electron injection layer is desirably a very thin film, and although depending on the constituent material, the layer thickness is preferably in the range of 1 nm to 10 μm.

(3.4.2: Hole transport layer)
The hole transport layer (HTL) is made of a hole transport material having a function of transporting holes. In a broad sense, the hole injection layer and the electron blocking layer also have a function of a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.

  As the hole transport material, those described above can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amine compounds can be used. preferable.

  For the hole transport layer, known methods such as vacuum deposition, spin coating, casting, printing including ink jet, and LB (Langmuir Brodget, Langmuir Broadgett) are used as the hole transport material. Thus, it can be formed by thinning. Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Moreover, p property can also be made high by doping the material of a positive hole transport layer with an impurity. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer because an element with lower power consumption can be manufactured.

(3.4.3: Electron transport layer)
The electron transport layer (ETL) is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer structure or a stacked structure of a plurality of layers.

  In the electron transport layer having a single-layer structure and the electron transport layer having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), 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, bis (8-quinolinol) zinc (abbreviation: Znq), etc. and the central metal of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as a material for the electron transport layer.

  The electron transport layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, and an LB method. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

(3.4.4: blocking layer)
The blocking layer includes a hole blocking layer and an electron blocking layer, and is a layer provided as necessary in addition to the constituent layers of the organic functional layer unit 3 described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). Hole blocking (hole block) layer and the like.

  The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of an electron carrying layer can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense. The electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made. Moreover, the structure of a positive hole transport layer can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

[3.5: Sealing member]
Examples of the sealing means used for sealing the organic EL element include a method in which a flexible sealing member, a cathode, and a transparent base material are bonded with a sealing adhesive.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and it may be concave plate shape or flat plate shape. Further, transparency and electrical insulation are not particularly limited.

  Specifically, a thin film glass plate, a polymer plate, a film, a metal film (metal foil) having flexibility, and the like can be given. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal film include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

In the present invention, as the sealing member, a polymer film and a metal film can be preferably used from the viewpoint that the organic EL element can be thinned. Further, the polymer film has a water vapor transmission rate of 1 × 10 ⁻³ g / m ² .multidot.m at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% RH measured by a method according to JIS K 7129-1992. The oxygen permeability measured by a method according to JIS K 7126-1987 is preferably 1 × 10 ⁻³ ml / m ² · 24 h · atm (1 atm is 1.01325 × 10 ⁵ a Pa) equal to or lower than a temperature of 25 ± 0.5 ° C., water vapor permeability at a relative humidity of 90 ± 2% RH is preferably not more than ^{1 × 10 -3 g / m 2} · 24h.

  In the gap between the sealing member and the display area (light emitting area) of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorocarbon or silicon oil is injected in the gas phase and liquid phase. You can also Further, the gap between the sealing member and the display area of the organic EL element can be evacuated, or a hygroscopic compound can be sealed in the gap.

  Further, the organic EL element is transparent in a state that completely covers the light emitting functional layer unit and exposes the terminal portions of the anode (3) as the first electrode and the cathode (6) as the second electrode in the organic EL element. A sealing film can also be provided on the substrate.

  The sealing material as described above is provided in a state in which the terminal portions of the anode (3) as the first electrode and the cathode (6) as the second electrode in the organic EL element are exposed and at least the light emitting functional layer is covered. It has been.

[4. Configuration example of organic EL element]
Next, regarding the configuration example of the organic EL element according to the present invention, the configuration excluding Embodiment 1 described above with reference to FIGS. 2 and 3 will be described with reference to the drawings.

[4.1 Configuration Example 2 of Organic EL Element (Embodiment 2)]
FIG. 4 is a schematic cross-sectional view showing another example (embodiment 2) of the configuration of the organic EL element having one organic functional layer unit, and the configuration described in “2. Typical configuration of organic EL element”. (2), flexible substrate / underlayer / anode (eg, silver thin film electrode) / organic functional layer unit [organic functional layer group 1 / light emitting layer / organic functional layer group 2] / cathode / sealing member The configuration is shown.

  In the organic EL element (OLED) shown in FIG. 4, the anode (3), which is a transparent electrode, is formed of a silver thin film electrode, and silver atoms are uniformly arranged below the anode described in FIG. The underlayer (7) is provided.

  In such a configuration, the anode (3) which is a transparent electrode has a configuration containing a metal material or a metal oxide material having an amorphous structure, and the cathode is made of a light-impermeable material. That is, when the anode (3) on the light extraction side is a transparent electrode having a structure containing a metal material or a metal oxide material having an amorphous structure, high light transmittance and excellent flexibility of the electrode can be obtained. From the viewpoint of being able to.

[4.2: Configuration Example 3 of Organic EL Element (Embodiment 3)]
FIG. 5 is a schematic sectional view showing an example (embodiment 3) of a configuration of an organic EL element having two organic functional layer units, and the configuration described in “2. Typical configuration of organic EL element” (3 ), Flexible substrate / anode / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / intermediate electrode / organic functional layer unit 2 [organic functional layer group 1B / light emitting Layer B / Organic Functional Layer Group 2B] / Cathode / Sealing Member Configuration.

  In FIG. 5, the organic EL element (OLED) has the first electrode (3) and the second electrode (6) arranged on the flexible substrate (1) at positions facing each other. In the configuration shown in FIG. 5, the first electrode (3) is an anode that is a transparent electrode, and the second electrode (6) is a cathode.

  Between the 1st electrode (3, anode) and the 2nd electrode (6, cathode), the 1st organic functional layer unit (4-A) comprised from the organic functional layer containing a luminescent layer and the 2nd The organic functional layer unit (4-B) is sandwiched, and an intermediate electrode (5) having an independent connection terminal (not shown) is disposed between the organic functional layer units.

  Each of the anode (3) and the intermediate electrode (5) is wired with a lead wire (11-A), and by applying about 2 to 40 V as a drive voltage V1 to each connection terminal, the first organic function The layer unit (4-A) emits light. Similarly, between the intermediate electrode (5) and the cathode (6) is wired with a lead wire (11-B), and an organic functional layer unit is applied by applying about 2 to 40 V as a driving voltage V2 to each connection terminal. (4-B) emits light.

  Specifically, when driving the organic EL element (OLED), a driving voltage V1 applied between the anode (3) and the intermediate electrode (5), and a driving voltage V2 applied between the intermediate electrode (5) and the cathode (6). When a DC voltage is applied, the anode (3) is applied with a positive polarity, the cathode (6) is applied with a negative polarity, and is applied within a voltage range of 2 to 40 V, and further to the intermediate electrode (5). In this case, an intermediate voltage between the anode and the cathode is applied.

  The emitted light (L) emitted from the light emitting point (h) of each organic functional layer unit is taken out from the anode (3) side which is a transparent electrode. The light emitted to the cathode (6) side is reflected by the surface of the cathode (6), which is a reflective electrode, and is similarly extracted from the anode (3) side.

  In such a configuration, the anode (3) or the intermediate electrode (5) is a transparent electrode having a configuration containing a metal material or a metal oxide material having an amorphous structure, and all the electrodes are made of the above materials. The configuration is preferable. That is, the anode (3) and the intermediate electrode (5) on the light extraction side are transparent electrodes having a structure containing a metal material or a metal oxide material having an amorphous structure. From the viewpoint of obtaining high flexibility.

  By having such a laminated structure in which two organic functional layer units including the light emitting layer shown in FIG. 5 are laminated, and applying an organic EL element with high luminous efficiency to the organic EL treatment apparatus of the present invention, Light (L) in a specific wavelength range selected within a range of 400 to 2000 nm is emitted from the light emitting surface side of the flexible substrate (1) surface. As a result, it is possible to irradiate a specific narrowband wavelength of emitted light (L) that is uniform and has a high therapeutic effect to a wide range of treatment sites with little influence of heat generation. It can be expected to achieve a high therapeutic effect on the treatment site.

[4.3: Configuration Example 4 of Organic EL Element (Embodiment 4)]
FIG. 6 is a schematic cross-sectional view showing another example (embodiment 4) of an organic EL element having two organic functional layer units, and the structure described in “2. Representative structure of organic EL element”. Flexible substrate / underlayer / anode (for example, silver thin film electrode) / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / intermediate electrode / organic exemplified in (4) The structure of functional layer unit 2 [organic functional layer group 1B / light emitting layer B / organic functional layer group 2B] / cathode / sealing member is shown.

  The configuration shown in FIG. 7 is a configuration in which an underlayer (7) is formed between the flexible substrate (1) and the anode (3) with respect to FIG. In such a configuration, the anode (3) is formed of a thin silver thin film.

  In such a configuration, at least one of the anode (3) and the intermediate electrode (5) is a transparent electrode having a configuration containing a metal material or a metal oxide material having an amorphous structure, and the anode (3) and the intermediate electrode. It is preferable that all the electrodes of (5) are comprised with the said material. In other words, the anode (3) and the intermediate electrode (5) on the light extraction side are transparent electrodes having a structure containing a metal material or a metal oxide material having an amorphous structure. It is preferable from the viewpoint of obtaining flexibility.

[Configuration Example 5 of Organic EL Element: Embodiment 5]
FIG. 7 is a schematic cross-sectional view showing another example (embodiment 5) of the configuration of the organic EL element having two organic functional layer units, and the configuration described in “2. Typical configuration of organic EL element”. Flexible substrate / anode / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / underlayer / intermediate electrode (for example, silver thin film electrode) / organic exemplified in (5) The structure of functional layer unit 2 [organic functional layer group 1B / light emitting layer B / organic functional layer group 2B] / cathode / sealing member is shown.

  The configuration shown in FIG. 7 is a configuration in which an intermediate electrode (5) and a base layer (7) are formed in the lower part of FIG. In such a configuration, at least the intermediate electrode (5) is formed of a thin silver thin film.

  In such a configuration, at least one of the anode (3) and the intermediate electrode (5) is a transparent electrode having a configuration containing a metal material or a metal oxide material having an amorphous structure, and the anode (3) and the intermediate electrode. It is preferable that all the electrodes of (5) are comprised with the said material. In other words, the anode (3) and the intermediate electrode (5) on the light extraction side are transparent electrodes having a structure containing a metal material or a metal oxide material having an amorphous structure. It is preferable from the viewpoint of obtaining flexibility.

[Configuration Example 6 of Organic EL Element: Embodiment 6]
FIG. 8 is a schematic sectional view showing an example (embodiment 6) of a configuration of an organic EL element having three organic functional layer units. The configuration described in “2. Typical configuration of organic EL element” (6 ), Flexible substrate / anode / organic functional layer unit 1 [organic functional layer group 1A / light emitting layer A / organic functional layer group 2A] / underlayer 1 / intermediate electrode 1 (for example, silver thin film electrode) / organic Functional layer unit 2 [Organic functional layer group 1B / Light emitting layer B / Organic functional layer group 2B] / Underlayer 2 / Intermediate electrode 2 (for example, silver thin film electrode) / Organic functional layer unit 3 [Organic functional layer group 1C / Light emission The structure of layer C / organic functional layer group 2C] / cathode is shown.

  The configuration shown in FIG. 8 is a configuration in which three organic functional layer units are stacked with respect to FIG. 7, and an intermediate layer (5-1, 5-2) and a lower layer (7-1, 7-2). In such a configuration, at least the intermediate electrode (5) is formed of a thin silver thin film.

  In such a configuration, at least one of the anode (3) and the intermediate electrode (5-1, 5-2) includes a metal material or a metal oxide material having an amorphous structure, and the anode (3) And it is preferable that all the electrodes of the intermediate electrode (5-1, 5-2) are made of the above-mentioned material. That is, the anode (3) on the light extraction side and the intermediate electrode (5-1, 5-2) have a structure containing a metal material or a metal oxide material having an amorphous structure, so that high light transmittance and an electrode can be obtained. It is preferable from the viewpoint of obtaining excellent flexibility.

《Light therapy》
[Outline of phototherapy]
Next, an outline of a phototherapy method (hereinafter also referred to as a phototherapy method according to the present invention) using the phototherapy device of the present invention will be described.

  As described above, the phototherapy method or phototherapy in the present invention is a method for performing treatment by light irradiation, that is, so-called phototherapy for a specific disease, and the phototherapy device of the present invention is described above. It is the apparatus which irradiates the light ray effective for the phototherapy equipped with the organic EL element which concerns on this invention.

  For example, for relief of pain such as stiff shoulders and back pain and treatment of thinning hair, treatment by irradiation with red light or infrared light is performed. This infrared treatment is performed by, for example, irradiating the affected area with near-infrared light to increase blood flow by expanding blood vessels, suppressing excitement of the sympathetic nervous system, or activating cellular tissue to activate wounds. It promotes healing and acts on inflammatory cytokines and analgesics to bring about anti-inflammatory and analgesic effects. In particular, the near-infrared region in the vicinity of a wavelength of 800 to 900 nm that absorbs less water, hemoglobin, and melanin has excellent biological permeability, and can suppress inflammation and relieve pain by an action mechanism different from the thermal effect. Treatment of atopic dermatitis by blue or ultraviolet irradiation.

  Thus, for the treatment of various diseases, a method using light is referred to as phototherapy, and a treatment using a photochemotherapeutic agent together with light irradiation is referred to as photodynamic therapy (PDT). In this PDT, a photosensitive therapeutic agent known as a photochemotherapeutic agent is supplied to the treated area of the body from the outside or the inside.

  The phototherapy method according to the present invention can be applied to the treatment of any illness, syndrome, disease, symptom, or various illnesses that respond to phototherapy or cosmetic symptoms.

  Therapeutic diseases and cosmetic conditions to which phototherapy can be applied include, for example, skin diseases and skin-related symptoms including skin aging and cellulite, enlarged pores, oily skin, folliculitis, Precancerous actinic keratosis, skin damage, aging, bruised and sun-damaged skin, eyelids, skin ulcers (diabetic, pressure ulcer, venous stasis), rosacea acne, cellulite Light adjustment of sebaceous glands and surrounding tissues, scoring, acne scars and acne bacteria, inflammation, pain, trauma, mental and nervous system related diseases and symptoms, comedones, edema, Paget's disease, primary tumor and metastasis Sex tumors, connective tissue diseases, collagen treatment, fibroblasts, and fibroblast-derived cell levels in mammalian tissues, retinal irradiation, neoplastic diseases, neovascular diseases and hypertrophic diseases, inflammatory and allergic reactions, sweat, D Phosphorus sweat gland (sweat gland) or sweat from the apocrine gland and hyper-hydrosis, jaundice, vitiligo, ocular neovascular disease, bulimia nervosa, herpes zoster, seasonal affective disorder, depression, sleep disorder, skin Cancer, Kriegler-Nager disease, atopic dermatitis, diabetic skin ulcer, pressure ulcer, bladder infection, muscle pain relief, pain, joint stiffness, bacterial reduction, gingivitis, tooth whitening, teeth and mouth tissue Treatment, wound healing.

  The cosmetic symptoms are selected from acne, skin rejuvenation and skin wrinkles, cellulite and vitiligo, and psoriasis (mild, mild to severe, and severe).

[Wavelength applied to phototherapy]
The phototherapy device of the present invention is characterized in that the emission wavelength of the organic EL element is in the wavelength range of 400 to 2000 nm.

  Furthermore, the emission wavelength of the organic EL element is preferably in the range of 400 to 1000 nm, more preferably 400 to 950 nm, and particularly preferably 400 to 900 nm.

  One of the main effects of phototherapy is known to be able to alleviate, for example, stiffness and pain by irradiating the skin surface with light of various wavelengths. That is, stimulation of metabolism in mitochondria. After the phototherapy, the cells increase in metabolism, improve transmission, and improve resistance to good stress and the like.

  The organic EL device according to the present invention can be used for cell stimulation. A preferred wavelength or wavelength range for cell stimulation is 600 to 900 nm, more preferably 620 to 880 nm, and particularly preferably 650 to 870 nm. Examples of particularly preferred wavelengths for cell stimulation are 683.7 nm, 667.5 nm, 772.3 nm, 750.7 nm, 846 nm, and 812.5 nm.

  The wavelength or wavelength range applied for skin care and skin repair is preferably in the range of 400 to 800 nm, more preferably in the range of 450 to 750 nm, still more preferably in the range of 500 to 700 nm. Preferably it is the range of 580-640 nm.

  Moreover, as an organic EL element used for acne treatment, a combination of red light and blue light is particularly preferable. The red light is preferably selected from the range of 590 to 750 nm, more preferably 600 to 720 nm, and still more preferably 620 to 700 nm. Two additional wavelengths preferred for the treatment of acne are 633 nm and 660 nm.

  In the case of a comedone, it is particularly preferable to apply an organic EL element that emits light having a wavelength of 500 nm or a wavelength in the range of 500 to 700 nm.

  The wavelength for treatment or prevention of cellulite (subcutaneous fat) is in the range of 400 to 1000 nm, preferably in the range of 400 to 900 nm, more preferably in the range of 450 to 900 nm, and particularly preferably in the range of 500 to 850 nm. It is.

  In addition, the wavelength for treatment or prevention of skin aging and the reduction or prevention of wrinkle formation is in the range of 400 to 950 nm. This wavelength is preferably in the range of 550 to 900 nm, more preferably in the range of 550 to 860 nm.

  Moreover, the organic EL element applied to skin rejuvenation emits light in the range of 700 to 1000 nm, preferably in the range of 750 to 900 nm, more preferably in the range of 750 to 860 nm, and particularly preferably in the range of 800 to 850 nm. It is an organic EL element.

  The wavelength for treatment and prevention of skin redness is in the range of 460 to 660 nm. The wavelength is preferably in the range of 500 to 620 nm, more preferably in the range of 540 to 580 nm. One particularly preferred wavelength for this purpose is 560 nm.

  The wavelength for treatment and prevention of dermatitis is in the range of 470 to 670 nm. The wavelength is preferably in the range of 490 to 650 nm, more preferably in the range of 530 to 610 nm. Two particularly preferred wavelengths for this purpose are 550 nm and 590 nm.

  Moreover, the wavelength for the treatment and prevention of atopic eczema is in the range of 470 to 670 nm. The wavelength is preferably in the range of 490 to 650 nm, more preferably in the range of 530 to 610 nm.

  The wavelength used for the treatment of edema is preferably in the range of 760 to 940 nm, more preferably in the range of 780 to 920 nm, still more preferably in the range of 800 to 900 nm, and particularly preferably in the range of 820 to 880 nm. .

  Moreover, the phototherapy device of the present invention can be used to treat a wound. Preferred wavelengths for the treatment of wounds by phototherapy are in the range of 600-950 nm, more preferably in the range of 650-900 nm, particularly preferred wavelengths are 660, 720, 880 nm.

  In addition, as described in JP-T-2002-51916, by irradiating 1917 nm infrared rays, the immune system is stimulated, so that no harm is caused to normal cells. Can be treated.

  Moreover, the wavelength for the treatment and prevention of nervous system and mental diseases and symptoms is in the range of 350 to 600 nm. The wavelength is preferably in the range of 400 to 550 nm, more preferably in the range of 440 to 500 nm. Two preferred wavelengths for this purpose are 460 nm and 480 nm.

[Photodynamic therapy (PDT)]
In the phototherapy method using the phototherapy device of the present invention, it is preferable to apply photodynamic therapy (PDT) using a photochemotherapeutic agent together with light irradiation by an organic EL element.

  PDT provides a topical or internal use of a photosensitive therapeutic agent known as a photopharmacological agent to the region of the body to be treated. Next, in this region, the photochemotherapy agent is activated by radiating light having an appropriate wavelength and intensity with the phototherapy device of the present invention. For example, a method of treating a tumor in which a photosensitizing substance as a photochemotherapeutic agent is taken into tumor cells and irradiated with light to kill the cells. More specifically, reactive oxygen is generated by introducing photosensitized fluorescent protein or the like into tumor cells or endothelial cells of new blood vessels in tumor tissue and irradiating with appropriate light. This active oxygen is a method in which tumor cells or tumor tissue are damaged and the tumor disappears.

  As a photochemotherapeutic agent (also referred to as a photosensitizing compound) applied to the photodynamic therapy (PDT), it is converted into a cytotoxic form upon irradiation with a photoactivating light beam, or is cytotoxic. A formulation containing a photosensitizing substance that gives rise to seeds.

  Photochemotherapeutic agents can be used for either systemic or local administration (eg, by delivery to the intestine, buccal, sublingual, gingival, palate, nasal, lung, vagina, rectum or eyeball). Photodynamic therapy formulations can also be provided in dosage forms suitable for oral or parenteral administration. Among these, photodynamic therapy preparations for topical administration include gels, creams, ointments, sprays, lotions, waxes, sticks, soaps, powders, tablets, films, vaginal suppositories, aerosols Formulated in any of drops, solutions, and conventional pharmaceutical forms in the art. In the case of topical administration or oral administration, absorption enhancers such as lubricants, moisturizers, emulsifiers, suspending agents, preservatives, sweeteners, flavoring agents, surface penetration aids and the like may be further included as necessary. .

  Examples of the photochemotherapeutic agent include 5-aminolevulinic acid hydrochloride (Crawford Pharmaceuticals), methylaminolevulinic acid (Metfix (registered trademark)), and Photocure (Photocure). ) And other topical agents. Also, for example, Photofin® (Photofin®) (from Axcan) and Foscan® (Fosscan®) (from Biolittech Ltd) There are injection drugs mainly used for malignant diseases. The drug is often applied in an inactive form, which is metabolized to a photosensitive photochemotherapeutic agent.

[Other functions of phototherapy device]
Various functions can be imparted to the phototherapy device of the present invention as needed together with the organic EL element described above.

For example,
1) A method of providing a function of automatically turning off the device when an organic EL element generates heat or overheats by installing an “overdoing prevention timer” for preventing excessive light irradiation,
2) An adhesive layer is provided on the side of the organic EL element that faces the affected area, and a function of attaching to the affected area is provided, and a therapeutic agent, menthol as a shipping agent, aroma using fever, acupuncture, etc. are applied to the adhesive layer. A method of containing,
3) A method in which a sheet having a fine hole is placed on the surface side in contact with the affected part with a slight gap from the organic EL element in order to prevent the affected part from being swollen. At this time, in order to impart a light irradiation effect to the formed hole portion, it is preferable that the configuration has a light extraction film and an internal scattering layer.
4) To have a toning function for changing the emission color of the organic EL element at the set time in order to notify the completion of phototherapy;
5) A function that can switch the light irradiation intensity without changing the color tone of the emitted light,
6) The provision of a waterproof function that can be used safely even in an environment where water is used,
7) As an organic EL element, it has a wide emission area and high emission uniformity (for this function, it is effective to apply a grid electrode)
Etc.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1
<< Production of organic EL element >>
[Production of Organic EL Element 1]
According to the following method, the organic EL element 1 having the configuration shown in FIGS. 2 and 3 was produced.

(Preparation of flexible base material with gas barrier layer)
As a flexible substrate, a polyethylene naphthalate film (a film made by Teijin DuPont Co., Ltd., hereinafter abbreviated as PEN) is used, and the entire surface on the side where the first electrode (transparent electrode, anode) is formed is disclosed in JP-A-2004-68143. An inorganic gas barrier layer composed of SiO _x is continuously formed on a flexible substrate (PEN) so as to have a thickness of 500 nm using an atmospheric pressure plasma discharge treatment apparatus having a configuration described in the publication. And the flexible base material with a gas barrier layer was produced.

(Formation of anode 1)
A flexible base material on which a gas barrier layer was formed was attached to an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, base material temperature 150 ° C., formation rate 5 nm / second, ITO (indium tin oxide) was DC pulse sputtered to have a layer thickness of 150 nm to produce an anode 1 as a transparent electrode made of ITO. The target-substrate distance was 86 mm.

  As a result of performing XRD analysis (X-ray diffraction method) on the anode 1 composed of the ITO formed above using an X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation, a specific diffraction line peak indicating crystallinity is obtained. It was recognized and confirmed to be a crystalline ITO film.

(Formation of organic functional layer unit)
An organic functional layer unit was formed on the anode 1 of the produced flexible substrate according to the procedure shown below. The flexible substrate was dried in a glove box having a dew point of −80 ° C. or less and an oxygen concentration of 1 ppm or less, and then installed in a vacuum evaporation apparatus for forming an organic functional layer unit without exposing it to the atmosphere from the glove box.

  Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

After depressurizing to a vacuum of 1 × 10 ⁻⁴ Pa, the deposition crucible containing compound M-2 was energized and heated, and deposited on the anode as the transparent electrode of the flexible substrate at a deposition rate of 0.1 nm / second. Then, a hole injection transport layer having a thickness of 40 nm was formed.

  Next, the compound BD-1 and the compound H-1 are co-evaporated at a deposition rate of 0.1 nm / second so that the concentration of the compound BD-1 is 5% by volume, and fluorescence that emits blue light with a thickness of 15 nm. A light emitting layer was formed.

  Next, the compound GD-1, RD-1 and compound H-2 were deposited at a deposition rate of 0.1 nm so that the compound GD-1 had a concentration of 17% by volume and RD-1 had a concentration of 0.8% by volume. The phosphorescent light emitting layer having a thickness of 15 nm and having a yellow color was formed.

  Thereafter, Compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 30 nm.

  Further, LiF was formed to a thickness of 1.5 nm, and then aluminum was deposited to a thickness of 110 nm to form a cathode (reflecting electrode, light impermeability).

  The compounds M-2, BD-1, H-1, GD-1, RD-1 and H-2 are compounds having the following structures.

(Production of sealing structure)
An organic EL element 301 was manufactured by pasting and sealing a sealing film so as to cover the formed anode to cathode.

  An adhesive was applied to a non-alkali glass substrate having a thickness of 0.7 mm and dried at 120 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A 50 μm-thick polyethylene terephthalate obtained by bonding a 100 μm-thick aluminum foil to this adhesive layer was used as a sealing film. After leaving this sealing film in a nitrogen atmosphere for 24 hours or more, the release sheet was removed, and the conductive film of the conductive film was bonded to cover the conductive layer with a vacuum laminator heated to 80 ° C. Furthermore, it heated and sealed for 30 minutes at 120 degreeC, and the organic EL element 1 was produced.

[Production of Organic EL Element 2]
In the production of the organic EL element 1, an organic EL element 2 was produced in the same manner except that the anode 2 formed by the following method was used instead of the anode 1.

(Formation of anode 2)
On the flexible base material on which the gas barrier layer is formed, a coating liquid for forming an anode 2 having the following composition is applied by a die coater and then dried to form an anode 2 composed of a conductive polymer having a thickness of 100 nm. did. During the drying process, radiant heat transfer drying using an infrared heater was performed for 5 minutes.

<Preparation of coating solution for forming anode 2>
Clevios PH1000 (PEDOT / PSS made by Heraeus, solid content concentration 1.2%) 70 parts by mass Ethylene glycol 15 parts by mass Ethylene glycol monobutyl ether 8 parts by mass Pure water 7 parts by mass [Preparation of organic EL element 3]
In the production of the organic EL element 1, an organic EL element 3 was produced in the same manner except that the anode 3 formed by the following method was used instead of the anode 1.

(Formation of anode 3)
The flexible base material on which the gas barrier layer was formed was attached to a vacuum tank, and after reducing the pressure to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. Thereby, the anode 3 made of silver having a film thickness of 7 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

[Production of Organic EL Element 4]
In the production of the organic EL element 3, an organic EL element 4 was produced in the same manner except that the following underlayer 1 was formed between the gas barrier layer of the flexible substrate and the anode 3.

(Formation of underlayer 1)
The flexible base material on which the gas barrier layer was formed was attached to a vacuum tank, and after reducing the pressure to 4 × 10 ⁻⁴ Pa, a heating boat containing the following compound 1 which is a nitrogen-containing compound was energized and heated. As a result, an underlayer having a film thickness of 3 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

[Production of Organic EL Element 5]
In the production of the organic EL element 3, the organic EL element 5 was produced in the same manner except that the anode 5 was formed using aluminum having a thickness of 7 nm instead of silver as the metal compound for forming the anode.

[Production of Organic EL Element 6]
In the production of the organic EL element 1, the organic EL element 6 was formed in the same manner except that the anode 6 formed of amorphous ITO (a-ITO) by the following method was used instead of the anode 1 (crystalline ITO). Produced.

(Formation of anode 6)
A flexible base material on which a gas barrier layer is formed is attached to an L-430S-FHS sputtering apparatus manufactured by Anelva, Inc. Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.) at a forming rate of 5 nm / second. Then, ITO (indium tin oxide) was DC pulse sputtered to have a layer thickness of 150 nm, and an anode 6 that was a transparent electrode made of amorphous ITO (a-ITO) was produced. The target-substrate distance was 86 mm.

  As a result of XRD analysis (X-ray diffraction method) using the X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation, the anode 6 composed of the a-ITO formed as described above was measured. Only a halo pattern was observed, and it was confirmed that the amorphous structure (amorphous structure) was in a state where a specific diffraction line peak indicating crystallinity was not exhibited.

[Production of Organic EL Element 7]
In the production of the organic EL element 6, the anode 7 was replaced with amorphous ITO (a-ITO), and the anode 7 that was a transparent electrode formed by amorphous IZO (a-IZO) produced by the following method was used. Except for this, the organic EL element 7 was produced in the same manner.

(Formation of anode 7)
A flexible base material on which a gas barrier layer is formed is attached to an L-430S-FHS sputtering apparatus manufactured by Anelva, Inc. Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.) at a forming rate of 5 nm / second. Then, IZO (indium zinc oxide) was DC pulse sputtered to have a layer thickness of 150 nm to produce an anode 7 which was a transparent electrode made of amorphous IZO (a-IZO). The target-substrate distance was 86 mm.

  As a result of XRD analysis (X-ray diffraction method) using the X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation, the anode 7 composed of the a-IZO formed as described above was measured. Only a halo pattern was observed, and it was confirmed that the amorphous structure (amorphous structure) was in a state where a specific diffraction line peak indicating crystallinity was not exhibited.

[Production of Organic EL Element 8]
In the production of the organic EL element 6, the anode 8 was replaced with amorphous ITO (a-ITO), and the anode 8 that was a transparent electrode formed by amorphous ZnO (a-ZnO) produced by the following method was used. Except for the above, an organic EL element 8 was produced in the same manner.

(Formation of anode 8)
A flexible base material on which a gas barrier layer is formed is attached to an L-430S-FHS sputtering apparatus manufactured by Anelva, Inc. Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.) at a forming rate of 5 nm / second. Then, ZnO (zinc oxide) was DC pulse sputtered to have a layer thickness of 150 nm to produce an anode 8 that was a transparent electrode made of amorphous ZnO (a-ZnO). The target-substrate distance was 86 mm.

  As a result of XRD analysis (X-ray diffractometry) using the X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation, the anode 8 composed of the a-ZnO formed as described above was measured. Only a halo pattern was observed, and it was confirmed that the amorphous structure (amorphous structure) was in a state where a specific diffraction line peak indicating crystallinity was not exhibited.

[Production of Organic EL Element 9]
In the production of the organic EL element 1, an organic EL element 9 was produced in the same manner except that the anode 9 formed by the following method was used instead of the anode 1.

(Formation of anode 9: grid-shaped electrode)
The grid for forming the anode 9 was formed by the following inkjet method.

  As a coating solution containing silver nanoparticles, a nanopaste for inkjet NPS-JL (manufactured by Harima Chemicals) is used, and a thin metal wire having a line width of 50 μm and an interval of 1 mm is striped on a flexible substrate on which a gas barrier layer is formed. Formed into a shape. The coating liquid was applied in layers so that a sufficient height was obtained. For coating, a desktop robot SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an ink jet head KM512SHX manufactured by Konica Minolta Co., Ltd. was used, and this was controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta Co., Ltd.).

Using a Pulse Forge 1300 manufactured by Nova Centrix, firing was performed by irradiating with xenon light to form a grid. Xenon light was irradiated by pulse light emission of 250 μs at a cycle of 500 μs, and the irradiation amount was adjusted so that the applied energy was 1500 mJ / cm ² .

  The size of the fine metal wires of the formed grid was measured several times by changing the position with a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100 (manufactured by Nihon Beco). The average value of the line width was 50 μm and the height The average value of was 1.0 μm.

  Next, a coating solution for forming a conductive polymer layer having the following composition was applied on the formed grid by a die coater, and then dried to coat the conductive polymer layer having a thickness of 100 nm to form an anode 9. . During the drying process, radiant heat transfer drying using an infrared heater was performed for 5 minutes.

<Preparation of coating solution for forming conductive polymer layer>
Clevios PH1000 (PEDOT / PSS manufactured by Heraeus Co., Ltd., solid content concentration 1.2%) 70 parts by mass Ethylene glycol 15 parts by mass Ethylene glycol monobutyl ether 8 parts by mass Pure water 7 parts by mass [Preparation of organic EL element 10]
In the production of the anode 9 of the organic EL element 9, the conductive layer formed on the grid-shaped electrode is replaced with a conductive polymer layer, and an amorphous ITO layer (a-ITO, electrode used for forming the organic EL element 6) An organic EL device 10 was produced in the same manner except for changing to 6).

[Production of Organic EL Element 11]
In the production of the anode 9 of the organic EL element 9, the conductive layer formed on the grid-shaped electrode is replaced with the conductive polymer layer, and the amorphous IZO layer (a-IZO, electrode) used for forming the organic EL element 7 is used. An organic EL element 11 was produced in the same manner except for changing to 7).

[Production of Organic EL Element 12]
In the preparation of the anode 9 of the organic EL element 9, the conductive layer formed on the grid-shaped electrode is replaced with a conductive polymer layer, and the amorphous ZnO layer (a-ZnO, electrode) used for forming the organic EL element 8 is used. An organic EL device 12 was produced in the same manner except for changing to 8).

[Production of Organic EL Element 13]
In the production of the organic EL element 1, an organic EL element 9 was produced in the same manner except that the anode 13 formed by the following method was used instead of the anode 1.

(Formation of anode 13: silver nanowire electrode)
On the flexible base material in which the gas barrier layer was formed, a silver nanowire dispersion was applied and dried to form a silver nanowire electrode. The application was performed using a die coater so that the distribution of silver nanowires was 0.25 g / m ² .

  A dispersion of silver nanowires was prepared with reference to the method described in the document “Adv. Mater., 2002, 14, 833-837”. Using ethylene glycol (manufactured by Kanto Chemical Co., Ltd.) as the reducing agent and polyvinylpyrrolidone (manufactured by Aldrich, average molecular weight of 1.3 million) as the form control agent and protective colloid agent, the steps of silver nucleation and particle formation were carried out. Separated to form silver nanowires. The reaction solution in which the silver nanowires are formed is subjected to desalting water washing treatment using an ultrafiltration membrane having a molecular weight cut off of 0.2 μm, and then the solvent is replaced with toluene to obtain a toluene dispersion of silver nanowires. It was.

  On the formed silver nanowire electrode, a coating solution for forming a conductive polymer layer having the following composition was applied by a die coater, followed by a drying treatment to coat the conductive polymer layer having a thickness of 100 nm to form a silver nanowire. A positive electrode 13 was formed. During the drying process, radiant heat transfer drying using an infrared heater was performed for 5 minutes.

<Preparation of coating solution for forming conductive polymer layer>
Clevios PH1000 (PEDOT / PSS made by Heraeus, solid content concentration 1.2%) 70 parts by mass Ethylene glycol 15 parts by mass Ethylene glycol monobutyl ether 8 parts by mass Pure water 7 parts by mass [Preparation of organic EL element 14]
In the preparation of the anode 13 of the organic EL element 13, the amorphous ITO layer (a-ITO, used for forming the organic EL element 6 was used instead of the conductive polymer layer instead of the conductive polymer layer formed on the silver nanowire electrode. An organic EL device 14 was produced in the same manner except that the electrode 6) was changed.

[Production of Organic EL Element 15]
In the preparation of the anode 13 of the organic EL element 13, the amorphous IZO layer (a-IZO, used for forming the organic EL element 7 was used instead of the conductive polymer layer instead of the conductive layer formed on the silver nanowire electrode. An organic EL element 15 was produced in the same manner except that the electrode 7) was changed.

[Production of Organic EL Element 16]
In the production of the anode 13 of the organic EL element 13, the conductive layer formed on the silver nanowire electrode is replaced with a conductive polymer layer, and an amorphous ZnO layer (a-ZnO, An organic EL element 16 was produced in the same manner except that the electrode 8) was changed.

<< Evaluation of anode and organic EL element >>
[Evaluation of heat generation inhibition]
Wiring was applied to each of the organic EL devices produced above, and a constant current of 50 A / m ² was applied for 30 minutes continuously in an environment of 25 ° C. and 50% RH, and the surface temperature of the light emitting surface was measured with a non-contact infrared surface thermometer ( Measured by Keyence Co., Ltd., ultra-small / small spot infrared thermometer IT2-50), the surface temperature before energization is T ₁ , and the surface temperature after energization for 30 minutes is T _2. (T2-T1) was determined and the heat generation inhibition property was evaluated according to the following criteria.

A: Temperature increase width ΔT is less than 10 ° C. O: Temperature increase width ΔT is 10 ° C. or more and less than 20 ° C. Δ: Temperature increase width ΔT is 20 ° C. or more and less than 30 ° C. ×: Temperature Increase width ΔT is 30 ° C. or more [Evaluation of disconnection resistance]
After wiring was performed on each of the produced organic EL elements, the following bending test was performed.

<Bending test>
・ Test environment 25 ℃, 50% RH
・ Bending angle R = 10mm
・ Number of bendings: 100 times ・ Bending direction Two conditions where the light-emitting surface side is outside and inside are set to bend number of times ・ Bending speed: 60 times / minute <Confirmation of disconnection>
In an environment of 25 ° C. and 50% RH, a constant current of 50 A / m ² was applied, voltage V ₁ before the bending test and voltage V ₂ after the bending test were measured, and a voltage difference ΔV (V ₂ −V ₁ ) was obtained, and the heat insulation resistance was evaluated according to the following criteria.

◎: Voltage difference ΔV is less than 0.5V ○: Voltage difference ΔV is 0.5V or more and less than 1.0V Δ: Voltage difference ΔV is 1.0V or more and less than 2.0V × : Voltage difference ΔV is 2.0 V or more or disconnection [Evaluation of conductivity]
In the production of each organic EL element, the sheet resistance value (Ω / □) of the anode surface of the sample formed up to the anode is compliant with JIS-K7194 using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Then, the measurement was performed by a 4-terminal 4-probe method constant current application method, and the conductivity was evaluated according to the following criteria.

◎: Sheet resistance value is less than 30Ω / □ ○: Sheet resistance value is 30Ω / □ or more and less than 100Ω / □ △: Sheet resistance value is 100Ω / □ or more and less than 200Ω / □ × : The sheet resistance value is 200Ω / □ or more. Table 1 shows the results obtained as described above.

  As is clear from the results shown in Table 1, the organic EL device having a transparent electrode that satisfies the conditions specified in the present invention is smaller in the temperature rise width of the radiation surface during light emission than the comparative example, and is not bent. On the other hand, it can be seen that there is no voltage rise or disconnection, it has excellent conductivity, and is effective as a surface-emitting light source for a phototherapy device.

  Using a phototherapy device equipped with each of the organic EL elements produced as a surface emitting light source for treatment, the patient's head, neck, shoulder, wrist, arm, abdomen, thigh, knee, ankle, instep, etc. As a result of verifying the phototherapy effect on the affected part having various shapes, the phototherapy device of the present invention can be accurately fitted to the shape of the affected part due to its excellent flexibility, and has a high phototherapy effect We were able to confirm that this is a device for phototherapy that has low fever during phototherapy, is safe and free of worry about burns, etc., and can stably obtain high therapeutic effects. .

Example 2
In the configuration of the organic EL element in Example 1, the configuration shown in FIGS. 2 and 3 is the same except that the two organic functional layer units shown in FIGS. 5 and 6 are changed to a configuration through an intermediate electrode. Each organic EL element 21-36 was produced.

  The organic EL elements 1 to 3 and 5 to 16 described in Example 1 are configured as illustrated in FIG. 5, and the anode (3) and the intermediate electrode (5) are configured by the electrodes described in Example 1, respectively. Organic EL elements 21 to 23 and 25 to 36 were produced.

  Moreover, about the organic EL element 4 of Example 1, it was set as the structure of FIG. 6, and the intermediate electrode (5) was formed with the silver thin film electrode. Organic functional layer units 4-A and 4-B were prepared by laminating two organic functional layer units described in Example 1 with an intermediate electrode interposed therebetween to produce an organic EL element 24.

  As a result of performing the evaluation and the method described in Example 1 for the organic EL elements 21 to 36 produced as described above, the organic EL element that satisfies the conditions defined in the present invention has a higher light irradiation effect than Example 1. As in Example 1, it can be obtained and has excellent heat generation suppression and disconnection resistance, has high conductivity, and is provided in a phototherapy device, so that it has excellent flexibility and shape. It is possible to accurately fit the shape of the affected area of the skin, and to obtain a high light treatment effect, and to produce a safe and stable high treatment effect with less fever during phototherapy, without worrying about burns, etc. We were able to confirm that this is a phototherapy device that can be used.

DESCRIPTION OF SYMBOLS 1 Flexible base material 2 Affected part 3 Anode (1st electrode)
4, 4-A, 4-B Organic functional layer unit 5, 5-1, 5-2 Intermediate electrode 6 Cathode (second electrode)
7, 7-1, 7-2 Underlayer 11, 11-A, 11-B, 11-C Lead wire 12 Light emitting unit 13 Adhesive layer for sealing 14 Flexible sealing substrate 22 Organic functional layer group 1
23 Light emitting layer 24 Organic functional layer group 2
OLED organic EL element EIL electron injection layer ETL electron transport layer HIL hole injection layer HTL hole transport layer h emission point L emission light V1, V2, V3 voltage

Claims (6)

A phototherapy device comprising an organic electroluminescence element as a surface light source on a flexible substrate,
The emission wavelength of the surface-emitting light source is in a wavelength range of 400 to 2000 nm,
The transparent electrode which comprises the said organic electroluminescent element contains the metal oxide material which has a metal material or an amorphous structure, and has flexibility, The phototherapy apparatus characterized by the above-mentioned.   2. The phototherapy device according to claim 1, wherein the metal oxide material is an amorphous indium oxide compound, an amorphous zinc oxide compound, or an amorphous tin oxide compound.   The phototherapy device according to claim 1 or 2, wherein the metal oxide material is amorphous indium tin oxide, amorphous indium zinc oxide, or amorphous zinc oxide.   The phototherapy device according to claim 1, wherein the metal material is silver or aluminum.   The transparent electrode constituting the organic electroluminescence element has a metal electrode layer mainly composed of silver and a base layer containing a substance having an interaction with silver at a position adjacent to the metal electrode layer. The device for phototherapy according to claim 1 or 4, wherein   The phototherapy device according to any one of claims 1 to 5, wherein a photochemotherapeutic agent is used together with the organic electroluminescence element.

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