Organic electroluminescent sheet for photocosmetic or phototherapy

Abstract

To provide a light irradiation sheet for photocosmetic or phototherapy, which has excellent skin-following properties and a comfortable fit. [Solution] An organic electroluminescent sheet for use in photocosmetic or phototherapy, characterized in that the organic electroluminescent sheet has a structure in which multiple layers are laminated on a sheet-like flexible substrate made of a resin material with the surface coated with epoxy resin, and is composed of organic electroluminescent elements with a thickness of 10 to 100 μm.

Description

[Technical field]

[0001] The present invention relates to an organic electroluminescent sheet for photocosmesis or phototherapy, more specifically to an organic electroluminescent sheet used for beauty treatment or treatment of injury or disease by irradiating light to the skin. [Background technology]

[0002] Attempts have been made to utilize light irradiation of the skin for beauty and the treatment of injuries and diseases, and for example, a beauty device that irradiates light onto the skin for the purpose of removing blemishes and wrinkles by utilizing the action of light on cells has been disclosed (see Patent Documents 1 and 2). Such beauty devices include a device that is used by bringing the light irradiating device close to the skin as in Patent Document 1, and a device that is used by wearing a mask with light-emitting diodes on the face as in Patent Document 2, but since the skin is uneven and the condition of the skin varies depending on the part, there are problems with these devices in that it is difficult to irradiate light evenly onto the skin or adjust the light to be irradiated according to the condition of the skin.

[0003] In response to such problems, there have been proposed portable devices that emit light using organic light-emitting semiconductors and are adapted to conform to the surface of the area to be treated with light, light treatment patches that conform to non-planar parts of the patient's body, and sealed bodies of biological light irradiation devices that have a biological light irradiation device having a flexible substrate and a light-emitting element containing an organic semiconductor or quantum dots in a protective bag (see Patent Documents 3 to 5). In addition, there has been proposed a method of obtaining cosmetic or therapeutic effects by applying a sheet containing an organic electroluminescent element to the skin and irradiating it with light to activate the skin (see Patent Document 6, Non-Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-154229 A [Patent Document 2] JP 2005-27702 A [Patent Document 3] Patent No. 4651281 [Patent Document 4] International Publication No. WO 00 / 015296 [Patent Document 5] International Publication No. WO 17 / 038655 [Patent Document 6] JP 2015-142717 A [Non-patent literature]

[0005] [Non-Patent Document 1] Yongmin Jeon and 7 others, "Advanced Materials Technologies", 2018, 1700391 [Non-Patent Document 2] Tomoyuki Yokota and 9 others, "Science Advances", 2016, No. 2, e1501856 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, various light irradiation devices have been proposed for use in photocosmetic and phototherapy applications. However, none of these devices are satisfactory in terms of their ability to conform to uneven skin and their wearing comfort, and there is room for improvement.

[0007] The present invention has been made in consideration of the above-mentioned current situation, and has an object to provide a light-irradiation sheet for photocosmesis or phototherapy that has excellent conformability to the skin and a comfortable fit. [Means for solving the problem]

[0008] The present inventors have studied a light-irradiating sheet having excellent skin-following properties and wearing comfort, and have found that by using an organic electroluminescent element having a thickness of 10 to 100 μm and a structure in which multiple layers are laminated on a sheet-like flexible substrate as a light source, a light-irradiating sheet having excellent skin-following properties and wearing comfort can be obtained. Furthermore, the present inventors have also found that by using an organic electroluminescent element having a so-called inverted structure, which has a structure in which multiple layers are laminated between a cathode and an anode formed on a sheet-like flexible substrate, as the organic electroluminescent element, a sheet containing an organic electroluminescent element having excellent element life can be obtained, and have arrived at the present invention.

[0009] That is, the present invention relates to an organic electroluminescent sheet for use in photocosmetic or phototherapy, characterized in that the organic electroluminescent sheet has a structure in which multiple layers are laminated on a sheet-like flexible substrate and is composed of organic electroluminescent elements having a thickness of 10 to 100 μm.

[0010] The organic electroluminescent device preferably has a structure in which a plurality of layers are laminated between a cathode and an anode formed on a sheet-like flexible substrate.

[0011] The organic electroluminescent device preferably has a metal oxide layer between a cathode and an anode formed on a sheet-like flexible substrate.

[0012] The organic electroluminescent sheet preferably further includes a thin-film battery.

[0013] The organic electroluminescent sheet preferably has a thickness of 650 μm or less.

[0014] The present invention also relates to a photocosmetic device comprising the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention.

[0015] The present invention also relates to a phototherapy device comprising the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention. Effect of the Invention

[0016] The organic electroluminescent sheet for photocosmesis or phototherapy of the present invention has high conformability to the skin and is comfortable to wear, and can therefore be suitably used as a sheet that is applied to the skin for cosmetic purposes using light irradiation or for the treatment of injuries or diseases. [Brief description of the drawings]

[0017] [Figure 1] 1 is a diagram showing a laminate structure of an organic electroluminescent device 1 produced in Example 1. FIG. [Diagram 2] 1 is a graph showing voltage-luminance characteristics when a direct current voltage of 0 V to 5 V is applied to the organic electroluminescent device 1 produced in Example 1 in an argon atmosphere. [Diagram 3] 1 is a graph showing the current density-current efficiency characteristics when a direct current voltage of 0 V to 5 V is applied to the organic electroluminescent device 1 produced in Example 1 in an argon atmosphere. [Figure 4] 1 is a diagram showing an emission spectrum when a direct current voltage of 0 V to 5 V is applied to the organic electroluminescent device 1 produced in Example 1 in an argon atmosphere. [Diagram 5] 2 is a graph showing the results of measuring the surface temperature of the organic electroluminescent device 1 produced in Example 1 while it was continuously driven at a constant luminance of 5,000 cd / m2, which is equivalent to an irradiance of 10 mW / cm2. [Figure 6] 1 is a photograph of an organic electroluminescent device sheet prepared in an example and a comparative example to which an external extraction electrode is attached. [Figure 7] 1 is a photograph showing a state in which an organic electroluminescent element sheet prepared in an example or comparative example and an external extraction electrode are attached to the sheet and directly attached to the skin of a subject. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0019] The organic electroluminescent sheet for photocosmetic or phototherapy of the present invention has a structure in which a plurality of layers are laminated on a sheet-like flexible substrate, and is characterized in that it comprises an organic electroluminescent element having a thickness of 10 to 100 μm. By using an organic electroluminescent element, which is characterized by being thin and flexible, as the light source of a sheet for photocosmetic or phototherapy, it is possible to produce a light-emitting sheet that has high conformability to the skin and is comfortable to wear. The thickness of the organic electroluminescent element contained in the organic electroluminescent sheet for photocosmetic or phototherapy is preferably 10 to 100 μm, more preferably 10 to 80 μm, further preferably 10 to 50 μm, and particularly preferably 10 to 30 μm. The thickness of the organic electroluminescent device can be measured by a digital caliper.

[0020] <Organic electroluminescent device> The organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention preferably has a structure in which a plurality of organic compound layers are laminated between an anode and a cathode. The structure of the organic electroluminescent element of the present invention is not particularly limited, but it is preferable that the element has each layer of a cathode, an electron injection layer and / or an electron transport layer, a light-emitting layer, a hole transport layer and / or a hole injection layer, and an anode, adjacent to each other in this order. Each of these layers may be composed of one layer or two or more layers. In the organic electric field element having the above-mentioned configuration, when the element has only one of the electron injection layer and the electron transport layer, the one layer is laminated adjacent to the cathode and the light-emitting layer, and when the element has both the electron injection layer and the electron transport layer, these layers are laminated adjacent to the cathode, the electron injection layer, the electron transport layer, and the light-emitting layer in this order. When the element has only one of the hole transport layer and the hole injection layer, the one layer is laminated adjacent to the light-emitting layer and the anode, and when the element has both the hole transport layer and the hole injection layer, these layers are laminated adjacent to the light-emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

[0021] The organic electroluminescent element may be an element of a normal structure in which an anode is formed on a sheet-like flexible substrate, or an element of an inverted structure in which a cathode is formed on a substrate. However, it is preferable that the element be an element of an inverted structure in which a plurality of layers are stacked between a cathode and an anode formed on a sheet-like flexible substrate. When an organic electroluminescent sheet for photocosmetic or phototherapy is applied directly to the skin, the element is easily affected by water vapor emitted from the skin. An organic electroluminescent element having a so-called inverted structure, in which a cathode is formed on a substrate and multiple layers are laminated thereon, is more resistant to water vapor than an organic electroluminescent element having a normal structure in which an anode is formed on a substrate and multiple layers are laminated thereon, and therefore, even with a laminate structure having fewer layers and a thinner seal than an element having a normal structure, the element life required for application to the human body can be achieved. For this reason, by using an organic electroluminescent element having an inverted structure, an organic electroluminescent sheet having a required element life, excellent flexibility, and better skin conformability can be obtained.

[0022] The organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention is preferably an organic-inorganic hybrid organic electroluminescent element further having a metal oxide layer between the cathode and the anode. By using a metal oxide as the material of the element, it is possible to obtain an organic electroluminescent element having higher resistance to water vapor. The organic electroluminescence device of the present invention is an organic-inorganic hybrid organic electroluminescence device having a metal oxide layer between the anode and the cathode, and preferably has a light-emitting layer and an anode, an electron injection layer and, if necessary, an electron transport layer between the cathode and the light-emitting layer, and a hole transport layer and / or a hole injection layer between the anode and the light-emitting layer. The organic electroluminescence device of the present invention may have other layers between these layers, but is preferably an element composed only of these layers. That is, it is preferably an element in which the layers of the cathode, the electron injection layer, if necessary, the electron transport layer, the light-emitting layer, the hole transport layer and / or the hole injection layer, and the anode are laminated adjacent to each other in this order. Each of these layers may be one layer or two or more layers.

[0023] In the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention, the material for forming the light-emitting layer may be any compound that can normally be used as a material for a light-emitting layer, and may be a low molecular weight compound or a high molecular weight compound, or a mixture of these may be used. In the present invention, a low molecular weight material means a material that is not a high molecular weight material (polymer), and does not necessarily mean an organic compound having a low molecular weight.

[0024] Examples of the polymeric material for forming the light-emitting layer include polyacetylene compounds such as trans-polyacetylene, cis-polyacetylene, poly(diphenylacetylene) (PDPA), and poly(alkyl, phenylacetylene) (PAPA); poly(para-phenylenevinylene) (PPV), poly(2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly(para-phenylenevinylene) (CN-PPV), poly(2-diphenylacetylene) (PPV), poly( ... Polyparaphenylenevinylene compounds such as methyloctylsilyl-paraphenylenevinylene) (DMOS-PPV) and poly(2-methoxy,5-(2'-ethylhexoxy)-paraphenylenevinylene) (MEH-PPV); polythiophene compounds such as poly(3-alkylthiophene) (PAT) and poly(oxypropylene)triol (POPT); poly(9,9-dialkylfluorene) (PDAF) and poly(dioctylfluorene) Polyfluorene compounds such as α,ω-bis[N,N'-di(methylphenyl)aminophenyl]-poly[9,9-bis(2-ethylhexyl)fluorene-2,7-diyl] (PF2 / 6am4), poly(9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co(anthracene-9,10-diyl); poly(para-phenylene) (PPP), poly(1,5-dialkoxy- ... Examples of such compounds include polyparaphenylene compounds such as poly(paraphenylene) (RO-PPP); polycarbazole compounds such as poly(N-vinylcarbazole) (PVK); polysilane compounds such as poly(methylphenylsilane) (PMPS), poly(naphthylphenylsilane) (PNPS), and poly(biphenylylphenylsilane) (PBPS); and boron compound-based polymer materials described in Japanese Patent Application Nos. 2010-230995 and 2011-6457.

[0025] Examples of low molecular weight materials for forming the light emitting layer include a three-coordinate iridium complex having 2,2'-bipyridine-4,4'-dicarboxylic acid as a ligand, factolis(2-phenylpyridine)iridium (Ir(ppy)3), 8-hydroxyquinoline aluminum (Alq3), tris(4-methyl-8-quinolinolato)aluminum(III) (Almq3), 8-hydroxyquinoline zinc (Znq2), (1,10-phenanthroline)-tris-(4,4,4-trifluoro-1-(2-thienyl)-butane-1,3-dionate)europium(III) (Eu(TTA)3(phen)), and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine. Various metal complexes such as platinum(II); benzene-based compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB); naphthalene-based compounds such as naphthalene and Nile Red; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene and 6-nitrochrysene; perylene-based compounds such as perylene and N,N'-bis(2,5-di-t-butylphenyl)-3,4,9,10-perylene-di-carboximide (BPPC); coronene-based compounds such as coronene; anthracene-based compounds such as anthracene and bisstyrylanthracene; pyrene-based compounds such as pyrene; 4-(di-cyanomethylene)-2-methyl-6-(para-dimethylaminostyryl)-4H-pyran (DC pyran compounds such as M); acridine compounds such as acridine; stilbene compounds such as stilbene; thiophene compounds such as 2,5-dibenzoxazolethiophene; benzoxazole compounds such as benzoxazole; benzimidazole compounds such as benzimidazole; benzothiazole compounds such as 2,2'-(para-phenylenedivinylene)-bisbenzothiazole; butadiene compounds such as bistyryl(1,4-diphenyl-1,3-butadiene), tetraphenylbutadiene; naphthalimide compounds such as naphthalimide; coumarin compounds such as coumarin; perinone compounds such as perinone; oxadiazole compounds such as oxadiazole; aldazine compounds;Examples of suitable materials include cyclopentadiene compounds such as 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP); quinacridone compounds such as quinacridone and quinacridone red; pyridine compounds such as pyrrolopyridine and thiadiazolopyridine; spiro compounds such as 2,2',7,7'-tetraphenyl-9,9'-spirobifluorene; metal or non-metal phthalocyanine compounds such as phthalocyanine (HPc) and copper phthalocyanine; and boron compound materials described in JP-A-2009-155325, JP-A-2010-230995, and JP-A-2011-6458. In addition, products of Chemipro Chemicals such as KHLHS-04 and KHLDR-03 can also be used.

[0026] The average thickness of the light-emitting layer is not particularly limited, but is preferably from 10 to 150 nm, more preferably from 20 to 100 nm, and even more preferably from 40 to 100 nm. The average thickness of the light-emitting layer can be measured by a quartz crystal film thickness gauge in the case of a low molecular weight compound, and by a contact step gauge in the case of a high molecular weight compound.

[0027] When the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention has an electron transport layer, the material thereof may be any compound that can normally be used as a material for an electron transport layer, and these may be used in combination. Examples of compounds that can be used as materials for the electron transport layer include pyridine derivatives such as tris-1,3,5-(3'-(pyridin-3''-yl)phenyl)benzene (TmPyPhB), quinoline derivatives such as (2-(3-(9-carbazolyl)phenyl)quinoline (mCQ)), pyrimidine derivatives such as 2-phenyl-4,6-bis(3,5-dipyridylphenyl)pyrimidine (BPyPPM), pyrazine derivatives, phenanthroline derivatives such as bathophenanthroline (BPhen), triazine derivatives such as 2,4-bis(4-biphenyl)-6-(4'-(2-pyridinyl)-4-biphenyl)-[1,3,5]triazine (MPT), triazole derivatives such as 3-phenyl-4-(1'-naphthyl)-5-phenyl-1,2,4-triazole (TAZ), and oxazole derivatives. Examples of the organic silane derivatives include oxadiazole derivatives such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl-1,3,4-oxadiazole) (PBD), imidazole derivatives such as 2,2',2''-(1,3,5-benzotriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBI), aromatic ring tetracarboxylic acid anhydrides such as naphthalene and perylene, various metal complexes such as bis[2-(2-hydroxyphenyl)benzothiazolato]zinc (Zn(BTZ)2) and tris(8-hydroxyquinolinato)aluminum (Alq3), and organic silane derivatives such as silole derivatives such as 2,5-bis(6'-(2',2''-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy). One or more of these may be used. Among these, metal complexes such as Alq3 and pyridine derivatives such as TmPyPhB are preferred.

[0028] As the electron injection layer, a layer made of a nitrogen-containing film formed from a nitrogen-containing compound can be used. Examples of the nitrogen-containing compound that forms the layer made of the nitrogen-containing film include pyrrolidones such as polyvinylpyrrolidone, pyrroles such as polypyrrole, anilines such as polyaniline, and pyridines such as polyvinylpyridine, as well as compounds having a nitrogen-containing heterocycle such as pyrrolidines, imidazoles, piperidines, pyrimidines, and triazines, and amine compounds.

[0029] The nitrogen-containing compound is preferably a compound with a high nitrogen content, and is preferably a polyamine, which has a high ratio of the number of nitrogen atoms to the total number of atoms constituting the compound, and is therefore suitable for providing an organic electroluminescent device with high electron injection properties and driving stability. The polyamines are preferably those capable of forming a layer by coating, and may be low molecular weight compounds or high molecular weight compounds. As low molecular weight compounds, polyalkylene polyamines such as diethylenetriamine and pentamethyldiethylenetriamine are preferably used, and as high molecular weight compounds, polymers having a polyalkyleneimine structure are preferably used. In particular, polyethyleneimine is preferred. Among them, one of the preferred embodiments of the present invention is that the nitrogen-containing compound is polyethyleneimine or diethylenetriamine. Here, a low molecular weight compound means a compound that is not a high molecular weight compound (polymer), and does not necessarily mean a compound with a low molecular weight.

[0030] The average thickness of the nitrogen-containing film is not particularly limited, but is preferably 0.5 to 10 nm, more preferably 1 to 5 nm, and further preferably 1 to 3 nm. The average thickness of the light-emitting layer can be measured by a quartz crystal film thickness gauge in the case of a low molecular weight compound.

[0031] When the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention has a hole transport layer, the hole transporting organic material used as the hole transport layer may be any of various p-type polymeric materials and various p-type low molecular weight materials, either alone or in combination. Examples of p-type polymeric materials (organic polymers) include polyarylamines, fluorene-arylamine copolymers, fluorene-bithiophene copolymers, poly(N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophenes, polyhexylthiophene, poly(p-phenylenevinylene), polytinylenevinylene, pyrene formaldehyde resins, ethylcarbazole formaldehyde resins, or derivatives thereof. These compounds can also be used in mixtures with other compounds, such as polythiophene-containing mixtures such as poly(3,4-ethylenedioxythiophene / styrenesulfonic acid) (PEDOT / PSS).

[0032] Examples of the p-type low molecular weight material include arylcycloalkane compounds such as 1,1-bis(4-di-para-triaminophenyl)cyclohexane and 1,1'-bis(4-di-para-tolylaminophenyl)-4-phenyl-cyclohexane, 4,4',4''-trimethyltriphenylamine, N,N,N',N'-tetraphenyl-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD1), N,N'-diphenyl-N,N'-bis(4-methoxyphenyl)-1,1'-biphenyl-4,4'-diamine (TPD2), N,N,N',N'-tetrakis(4-methoxyphenyl) arylamine compounds such as N,N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (TPD3), N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD), TPTE; phenylenediamine compounds such as N,N,N',N'-tetraphenyl-p-phenylenediamine, N,N,N',N'-tetra(p-tolyl)-p-phenylenediamine, N,N,N',N'-tetra(meta-tolyl)-meta-phenylenediamine (PDA); carbazole compounds such as carbazole, N-isopropylcarbazole, and N-phenylcarbazole; stilbene compounds such as 4-di-p-tolylaminostilbene; xZ, triphenylmethane, triphenylmethane compounds such as m-MTDATA, pyrazoline compounds such as 1-phenyl-3-(para-dimethylaminophenyl)pyrazoline, benzine (cyclohexadiene) compounds, triazole compounds such as triazole, imidazole compounds such as imidazole, oxadiazole compounds such as 1,3,4-oxadiazole, 2,5-di(4-dimethylaminophenyl)-1,3,4-oxadiazole, anthracene compounds such as 9-(4-diethylaminostyryl)anthracene, fluorenone compounds such as 2,4,7-trinitro-9-fluorenone, 2,7-bis(2-hydroxy-3-(2-chlorophenylcarbamoyl)-1-naphthylazo)fluorenone, polya Examples of the compound include aniline-based compounds such as aniline, silane-based compounds, pyrrole-based compounds such as 1,4-dithioketo-3,6-diphenyl-pyrrolo-(3,4-c)pyrrolopyrrole, florene-based compounds such as florene, porphyrin-based compounds such as porphyrin and metal tetraphenylporphyrin, quinacridone-based compounds such as quinacridone, metallic or non-metallic phthalocyanine-based compounds such as phthalocyanine, copper phthalocyanine, tetra(t-butyl)copper phthalocyanine, and iron phthalocyanine, metallic or non-metallic naphthalocyanine-based compounds such as copper naphthalocyanine, vanadyl naphthalocyanine, and monochlorogallium naphthalocyanine, and benzidine-based compounds such as N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine and N,N,N',N'-tetraphenylbenzidine.

[0033] When the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention has an electron transport layer or a hole transport layer, the average thickness of these layers is not particularly limited, but is preferably 10 to 150 nm, more preferably 20 to 100 nm, and even more preferably 40 to 100 nm. The average thickness of the electron transport layer or hole transport layer can be measured by a quartz crystal film thickness meter in the case of a low molecular weight compound, and by a contact step gauge in the case of a high molecular weight compound.

[0034] When the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention has a metal oxide layer, it has a metal oxide layer between the cathode and the light-emitting layer, between the anode and the light-emitting layer, or both, but it is preferable to have a metal oxide layer between the cathode and the light-emitting layer and between the light-emitting layer and the anode. If the metal oxide layer between the cathode and the light-emitting layer is the first metal oxide layer, and the metal oxide layer between the anode and the light-emitting layer is the second metal oxide layer, it is preferable that the first metal oxide layer is used as an electron injection layer and the second metal oxide layer is used as a hole injection layer. An example of a preferred element configuration of the organic electroluminescent element of the present invention is a configuration in which a cathode, a first metal oxide layer, a layer made of a nitrogen-containing film, a light-emitting layer, a hole transport layer, a second metal oxide layer, and an anode are laminated adjacent to each other in this order. Note that an electron transport layer may be provided between the layer made of a nitrogen-containing film and the light-emitting layer as necessary. The importance of the metal oxide layer is higher for the first metal oxide layer, and the second metal oxide layer can be replaced by an organic material with an extremely deep lowest unoccupied molecular orbital, such as HATCN.

[0035] The first metal oxide layer is a layer consisting of a single metal oxide film, or a semiconductor or insulator laminated thin film layer which is a layer consisting of a single metal oxide film or a laminated and / or mixed layer of two or more metal oxides. The metal elements constituting the metal oxide are selected from the group consisting of magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, indium, gallium, iron, cobalt, nickel, copper, zinc, cadmium, aluminum, and silicon. Of these, it is preferable that at least one of the metal elements constituting the laminated or mixed metal oxide layer is a layer consisting of magnesium, aluminum, calcium, zirconium, hafnium, silicon, titanium, or zinc, and among them, it is preferable that the single metal oxide contains a metal oxide selected from the group consisting of magnesium oxide, aluminum oxide, zirconium oxide, hafnium oxide, silicon oxide, titanium oxide, and zinc oxide.

[0036] Examples of layers in which the above-mentioned single or two or more kinds of metal oxides are laminated and / or mixed include laminated and / or mixed combinations of metal oxides such as titanium oxide / zinc oxide, titanium oxide / magnesium oxide, titanium oxide / zirconium oxide, titanium oxide / aluminum oxide, titanium oxide / hafnium oxide, titanium oxide / silicon oxide, zinc oxide / magnesium oxide, zinc oxide / zirconium oxide, zinc oxide / hafnium oxide, zinc oxide / silicon oxide, and calcium oxide / aluminum oxide, and laminated and / or mixed combinations of three kinds of metal oxides such as titanium oxide / zinc oxide / magnesium oxide, titanium oxide / zinc oxide / zirconium oxide, titanium oxide / zinc oxide / aluminum oxide, titanium oxide / zinc oxide / hafnium oxide, titanium oxide / zinc oxide / silicon oxide, and indium oxide / gallium oxide / zinc oxide. Among these, IGZO, an oxide semiconductor that exhibits good characteristics as a special composition, and 12CaO·7Al2O3, an electride, are also included. The first metal oxide layer can be called an electron injection layer and also an electrode (cathode). In the present invention, those with a sheet resistance lower than 100 Ω / □ are classified as conductors, and those with a sheet resistance higher than 100 Ω / □ are classified as semiconductors or insulators. Therefore, thin films of ITO (tin-doped indium oxide), ATO (antimony-doped indium oxide), IZO (indium-doped zinc oxide), AZO (aluminum-doped zinc oxide), FTO (fluorine-doped indium oxide), etc., which are known as transparent electrodes, are highly conductive and do not fall into the category of semiconductors or insulators, and therefore do not correspond to one layer constituting the first metal oxide layer.

[0037] Furthermore, the first metal oxide layer may be a laminate of a metal oxide layer and a layer of a simple metal, so long as it contains a metal oxide layer. The elements constituting the metal oxide are as described above. Examples of metals that can be used for the layer of a simple metal include silver and palladium, and one or more of these can be used.

[0038] When the first metal oxide layer is a laminate of a metal oxide layer and a layer of a simple metal, it is preferable that the metal oxide layer and the layer of the simple metal are alternately laminated. In this case, the number of metal oxide layers and the layer of the simple metal is preferably two metal oxide layers and one simple metal layer. In other words, a structure in which one simple metal layer is sandwiched between two metal oxide layers is preferable.

[0039] The metal oxide forming the second metal oxide layer is not particularly limited, and one or more of vanadium oxide (VO), molybdenum oxide (MoO), tungsten oxide (WO), ruthenium oxide (RuO) and the like can be used. Among these, vanadium oxide or molybdenum oxide is preferable as the main component. When the second metal oxide layer is composed of vanadium oxide or molybdenum oxide as the main component, the second metal oxide layer has a better function as a hole injection layer that injects holes from the anode and transports them to the light-emitting layer or the hole transport layer. In addition, vanadium oxide or molybdenum oxide has a high hole transport property by itself, and therefore has the advantage of being able to suitably prevent the efficiency of hole injection from the anode to the light-emitting layer or the hole transport layer from decreasing. More preferably, it is composed of vanadium oxide and / or molybdenum oxide.

[0040] The average thickness of the first metal oxide layer is permissible from about 1 nm to several μm, but from the viewpoint of obtaining an organic electroluminescent device that can be driven at a low voltage, it is preferably 1 to 1000 nm, and more preferably 2 to 100 nm. The average thickness of the second metal oxide layer is not particularly limited, but is preferably 1 to 1000 nm, and more preferably 5 to 50 nm. The average thickness of the first metal oxide layer can be measured by a stylus step gauge or spectroscopic ellipsometry. The average thickness of the second metal oxide layer can be measured as it is deposited using a quartz crystal thickness gauge.

[0041] In the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention, the anode and cathode can be appropriately made of known conductive materials, but it is preferable that at least one of them is transparent for light extraction. Examples of known transparent conductive materials include ITO (tin-doped indium oxide), ATO (antimony-doped indium oxide), IZO (indium-doped zinc oxide), AZO (aluminum-doped zinc oxide), FTO (fluorine-doped indium oxide), etc. Examples of opaque conductive materials include calcium, magnesium, aluminum, tin, indium, copper, silver, gold, platinum, and their alloys. Of these, ITO, IZO, and FTO are preferable for the cathode. Of these, Au, Ag and Al are preferable for the anode. As described above, since metals generally used for anodes can be used for the cathode and anode, it is easy to realize the case where light is extracted from the upper electrode (top emission structure), and various electrodes can be selected and used for each electrode. For example, Al can be used for the lower electrode and ITO for the upper electrode.

[0042] The average thickness of the cathode is not particularly limited, but is preferably 10 to 500 nm, and more preferably 100 to 200 nm. The average thickness of the cathode can be measured by a stylus step gauge or spectroscopic ellipsometry. The average thickness of the anode is not particularly limited, but is preferably 10 to 1000 nm. More preferably, it is 30 to 150 nm. Even when an opaque material is used, the anode can be used as a top emission type or transparent type anode by setting the average thickness to, for example, about 10 to 30 nm. The average thickness of the anode can be measured during deposition using a quartz crystal thickness gauge.

[0043] In the organic electroluminescence device of the present invention, the method of forming the layer made of the organic compound is not particularly limited, and various methods can be appropriately used according to the characteristics of the material, but when the solution can be applied, the layer can be formed by various application methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, slit coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and inkjet printing. Among these, the spin coating and slit coating methods are preferred because the film thickness is easier to control. When no application is performed or the solvent solubility is low, suitable examples include vacuum deposition and ESDUS (Evaporative Spray Deposition from Ultra-dilute Solution) methods.

[0044] When the layer made of the organic compound is formed by applying a solution of the organic compound, examples of the solvent used to dissolve the organic compound include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate; ketone-based solvents such as methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), and cyclohexanone; alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), and glycerin; and ether-based solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), and diethylene glycol ethyl ether (carbitol). Examples of the organic solvent include cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and phenyl cellosolve; aliphatic hydrocarbon-based solvents such as hexane, pentane, heptane, and cyclohexane; aromatic hydrocarbon-based solvents such as toluene, xylene, and benzene; aromatic heterocyclic compound-based solvents such as pyridine, pyrazine, furan, pyrrole, thiophene, and methylpyrrolidone; amide-based solvents such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA); halogen compound-based solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane; ester-based solvents such as ethyl acetate, methyl acetate, and ethyl formate; sulfur compound-based solvents such as dimethyl sulfoxide (DMSO) and sulfolane; nitrile-based solvents such as acetonitrile, propionitrile, and acrylonitrile; and organic acid-based solvents such as formic acid, acetic acid, trichloroacetic acid, and trifluoroacetic acid, or mixed solvents containing these. Among these, non-polar solvents are suitable as the solvent, and examples thereof include aromatic hydrocarbon solvents such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, and tetramethylbenzene; aromatic heterocyclic compound solvents such as pyridine, pyrazine, furan, pyrrole, thiophene, and methylpyrrolidone; and aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane. These can be used alone or in combination.

[0045] The cathode, anode, and oxide layer can be formed by sputtering, vacuum deposition, sol-gel, spray pyrolysis (SPD), atomic layer deposition (ALD), vapor phase deposition, liquid phase deposition, and the like. Metal foil bonding can also be used to form the anode and cathode. These methods are preferably selected according to the characteristics of the material of each layer, and the fabrication method may be different for each layer. Among these, it is more preferable to form the second metal oxide layer using a vapor phase deposition method. According to the vapor phase deposition method, the organic compound layer can be formed cleanly and in good contact with the anode without destroying the surface, and as a result, the effect of having the second metal oxide layer as described above becomes more remarkable.

[0046] For the purpose of further improving the properties of the organic electroluminescent device, for example, a hole blocking layer, an electron blocking layer, etc. may be provided as necessary. As materials for forming these layers, materials usually used for forming these layers are used, and the layers can be formed by methods usually used for forming these layers.

[0047] In addition, after forming the last electrode of the laminated structure, a passivation layer for protecting the surface may be formed thereon. The material of the passivation layer may be any material that is usually used to form these layers. For example, the material of the hole transport layer and / or the material of the metal oxide layer described above may be used, but is not limited to this as long as the combination can maintain insulation.

[0048] The average thickness of the passivation layer is not particularly limited, but is preferably 20 to 300 nm, and more preferably 50 to 200 nm. The average thickness of the passivation layer can be measured as it is deposited using a quartz crystal thickness gauge.

[0049] The organic electroluminescent device uses a sheet-like flexible substrate. Examples of materials for the substrate include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate. Moreover, the above-mentioned resin materials may be coated on the surface with epoxy resin or the like and used as flexible substrates.

[0050] The average thickness of the substrate is preferably 10 to 150 μm, and more preferably 10 to 50 μm. The average thickness of the substrate can be measured by digital calipers.

[0051] The organic electroluminescent device may further have a sealing layer on the passivation layer. The material for forming the sealing layer may be the same as the material for the sheet-like flexible substrate, and the thickness of the sealing layer is preferably the same as the thickness of the sheet-like flexible substrate.

[0052] When sealing the organic electroluminescent element constituting the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention, a conventional method can be appropriately used as the sealing step. For example, a method of bonding a sealing container in an inert gas, a method of forming a sealing film directly on the organic electroluminescent element, etc. may be mentioned. In addition to these, a method of sealing a moisture absorbent may be used in combination. The organic electroluminescent device having the above-mentioned inverted structure does not require strict sealing as compared with the organic electroluminescent device having the forward structure, but may be sealed if necessary.

[0053] The organic electroluminescent device may be of a top emission type in which light is extracted from the side opposite to the side where the substrate is located, or of a bottom emission type in which light is extracted from the side where the substrate is located.

[0054] <Thin film battery> The organic electroluminescent sheet for photocosmesis or phototherapy of the present invention may be used in connection with an external power source, or may contain a thin-film battery within the sheet; however, if the sheet contains a thin-film battery, it can be used without connecting to an external power source, which improves portability, etc., and makes it easier to use. Thus, an organic electroluminescent sheet further comprising a thin-film battery is one of the preferred embodiments of the organic electroluminescent sheet for photocosmesis or phototherapy of the present invention.

[0055] As the thin-film battery, either a thin-film primary battery or a thin-film secondary battery can be used, and a thin-film lithium ion battery using a solid electrolyte can be used.

[0056] The positive electrode active material of the thin-film battery is not particularly limited, and may be, for example, one or more of lithium composite oxides such as LiCoO2, LiMnO2, LiFePO4, and LiCoPO4; and lithium-free metal sulfides such as TiS and MoS2.

[0057] The negative electrode active material of the thin-film battery is not particularly limited, and may be one or more of the following: carbon materials such as graphite; metal oxides such as V2O5; and materials capable of forming alloys with lithium, such as simple substances, alloys, and compounds of Si and Sn.

[0058] The solid electrolyte of the thin-film battery is not particularly limited, and examples thereof include Li3N, LiI, Li3PO4, LiPO 4-x N x and the like; and lithium-containing sulfides such as Li2S-SiS2, Li2S-P2S5, Li2S-B2S3, and other glassy solid electrolytes.

[0059] The above-mentioned thin-film battery preferably has a thickness of 450 μm or less. By using a thin-film battery with such a thickness, the thickness of the organic electroluminescent sheet of the present invention can be reduced, the organic electroluminescent sheet has better conformability to the skin, and the discomfort when applied to the skin can be reduced. The thickness of the thin-film battery is more preferably 100 to 300 μm, and further preferably 50 to 100 μm. The thickness of the thin-film battery can be measured using a digital multimeter and a vernier caliper.

[0060] The method for producing the thin-film battery is not particularly limited, but it can be produced, for example, by laminating a positive electrode, a solid electrolyte, and a negative electrode in this order on a substrate by sputtering.

[0061] <Other elements> The organic electroluminescent sheet for photocosmetic or phototherapy of the present invention may contain elements other than the organic electroluminescent element and the thin-film battery. Examples of the other elements include an adhesive layer or bonding layer between the skin and the sheet, a color filter layer for wavelength control, a buffer layer for improving light extraction, wiring and a power switch for electrical connection of each electronic component, packaging for appearance, etc. The organic electroluminescent sheet for photocosmetic or phototherapy of the present invention may contain one or more of these elements.

[0062] The organic electroluminescent sheet for photocosmetic or phototherapy of the present invention preferably has a thickness of 650 μm or less. As described above, the organic electroluminescent sheet for photocosmetic or phototherapy of the present invention may contain elements other than organic electroluminescent elements, and in such a case, if the thickness of the entire sheet is 650 μm or less, the sheet will have better conformability to the skin and will cause less discomfort when applied to the skin. The thickness of the organic electroluminescent sheet is more preferably 10 to 600 μm, and even more preferably 50 to 100 μm. The thickness of the organic electroluminescent sheet can be measured using a digital multimeter and calipers.

[0063] The organic electroluminescent sheet for photocosmetic or phototherapy of the present invention is a sheet that has high conformability to the skin and has an excellent element life, and therefore can be suitably used for photocosmetic applications aimed at removing blemishes and wrinkles on the skin, and for medical applications aimed at treating injuries and diseases. A photocosmetic device or phototherapy device comprising such an organic electroluminescent sheet for photocosmetic or phototherapy of the present invention also constitutes the present invention. EXAMPLES

[0064] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by mass".

[0065] 1. Preparation of organic electroluminescent device Example 1 Organic electroluminescent device 1 was produced by the method described below. [Process 1] As the substrate 1, a 25 μm thick PET film with a barrier layer purchased from Oike Kogyo Co., Ltd. was coated with SU-8 manufactured by Nippon Kayaku Co., Ltd. by spin coating, and baked on a hot plate heated to 100° C. [Process 2] The substrate 1 was set in a sputtering device, and a zinc oxide (ZnO) layer with an average thickness of 20 nm was formed on the substrate 1 by sputtering using zinc metal as a target, oxygen as a reactive gas, and argon as a carrier gas. The substrate was then set in a vacuum deposition device, and a silver layer with an average thickness of 8 nm was formed. The substrate was then set in the sputtering device again, and a zinc oxide layer with an average thickness of 2 nm was formed. The substrate 1 was then transferred to the atmosphere, and annealed on a hot plate at 100°C for 30 minutes, to form a transparent electrode 2 and an oxide layer 3. [Process 3] Next, polyethyleneimine manufactured by Nippon Shokubai Co., Ltd. was applied onto the oxide layer 3 by spin coating to form an electron injection layer 4. The average thickness of the electron injection layer 4 was 2 nm. [Step 4] Next, the substrate 1 on which each layer up to the electron injection layer 4 had been formed was fixed to a substrate holder of a vacuum deposition apparatus. In addition, KHLHS-04, KHLDR-03, and N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD) represented by the following formula (1), all of which were purchased from Chemipro Chemicals, were placed in alumina crucibles and set as deposition sources. The interior of the vacuum deposition apparatus was then filled with approximately 1×10 -5 The pressure was reduced to 20 Pa, and KHLHS-04 was evaporated to a thickness of 10 nm to form an electron transport layer 5. Next, KHLHS-04 and α-NPD were co-evaporated to a thickness of 15 nm with KHLDR-03 as the emitting dopant to form an emitting layer 6. Next, α-NPD was evaporated to a thickness of 40 nm to form a hole transport layer 7. Furthermore, molybdenum trioxide MoO3 was evaporated throughout the vacuum to form a hole injection layer 8 having a thickness of 10 nm. [Step 5] Next, aluminum (anode 9) was evaporated onto the substrate 1 on which the hole injection layer 8 had been formed, to a film thickness of 70 nm. [Step 6] Next, α-NPD was evaporated to a thickness of 100 nm onto the substrate 1 on which the anode 9 had been formed, and then zinc oxide was deposited to a thickness of 20 nm using a sputtering device, thereby obtaining a passivation layer 10. [Step 7] Next, the substrate 1 on which the passivation layer 10 had been formed was transported to a glove box, and TB1655 manufactured by ThreeBond and a 25 μm thick PET film with a barrier layer purchased from Oike Kogyo Co., Ltd. were laminated onto the substrate 1, and annealed for 1 hour on a hot plate heated to 90° C. to form a sealing layer 11, thereby obtaining "Element 1," an embodiment of the present invention. The thickness of the obtained element 1 was measured by a Mitutoyo Corporation Digimatic Indicator, ID-C112AB, and the total film thickness was 72 μm.

[0066] [ka]

[0067] Example 2 An organic electroluminescence device was produced by omitting [Step 7] of Example 1.

[0068] Example 3 An organic electroluminescence device was produced in the same manner as in Example 1, except that in [Step 1], a PET film with a barrier layer having a thickness of 50 μm was used instead of the PET film with a barrier layer having a thickness of 25 μm.

[0069] Comparative Example 1 An organic electroluminescence device was produced in the same manner as in Example 1, except that in [Step 1] and [Step 7], a PET film with a barrier layer having a thickness of 50 μm was used instead of the PET film with a barrier layer having a thickness of 25 μm.

[0070] Comparative Example 2 An organic electroluminescence device was produced in the same manner as in Example 1, except that in [Step 1] and [Step 7], a PET film with a barrier layer having a thickness of 75 μm was used instead of the PET film with a barrier layer having a thickness of 25 μm.

[0071] (Fabricated organic electroluminescent device) The total film thicknesses of the organic electroluminescent devices fabricated in Examples 1 to 3 and Comparative Examples 1 and 2, measured using a Mitutoyo Digimatic Indicator ID-C112AB, are summarized in Table 1.

[0072] [Table 1]

[0073] 2. Measurement of the luminescence characteristics of organic electroluminescent devices A voltage was applied to the element and a current was measured using a Keithley 2400 source meter. Emission luminance and EL spectrum were measured using a Topcon BM-7 and a spectroradiometer SR-3. The voltage-luminance characteristics, current density-current efficiency characteristics, and EL spectrum when a direct current voltage of 0 V to 5 V was applied to the organic electroluminescent element produced in Example 1 under an argon atmosphere are shown in Figs. 2, 3, and 4, respectively. Similar measurements were also carried out on the elements of Examples 2 and 3 and Comparative Examples 1 and 2, and the characteristics were similar to those of the element of Example 1.

[0074] 3. Measurement of surface temperature change during continuous constant brightness driving of organic electroluminescent devices Since the organic electroluminescence element is a heat generating element, there is a concern of low-temperature burns when it is used in direct contact with the skin. Among the elements produced in Examples 1 to 3 and Comparative Examples 1 and 2, the element produced in Example 1 is the shortest in distance to the skin, and there is a concern of low-temperature burns. Therefore, the organic electroluminescence element produced in Example 1 was used at an irradiance of 10 mW / cm, which is assumed to be used in practice. 2 Equivalent to 5,000cd / m 2 The surface temperature in contact with the skin was measured while the device was continuously operated at a constant brightness at 400°C. The measurements were performed using an infrared thermography camera (R300SR) manufactured by Nippon Avionics Co., Ltd. The data shown in Figure 5 was obtained, and it was found that the surface temperature did not exceed 36°C even with long-term use, and there was no risk of low-temperature burns.

[0075] 4. Evaluation test of organic electroluminescent sheet The conformability and adhesion of the organic electroluminescent sheet to the skin were evaluated by the following method.

[0076] The organic electroluminescent sheets produced in Examples 1 to 3 and Comparative Examples 1 and 2 were fitted with an external extraction electrode as shown in Fig. 6, and the sheets were directly attached to the skin of a subject as shown in Fig. 7. The external extraction electrode was connected to an external electrode, and the sheets were allowed to emit light for one hour. The subjects were randomly selected based on their gender and age.

[0077] (Skin compatibility test (sensory test)) As an index of conformability after application of the organic electroluminescent sheet, the discomfort and ease of movement at the application site (mainly due to a feeling of tightness or restriction at that site) were evaluated according to the following criteria. The average evaluation results by 10 subjects are shown in Table 2. [Evaluation Criteria] 5. No discomfort when worn and easy to move around in 4: Somewhat uncomfortable to wear, somewhat easy to move around in 3: Neither 2: Feels uncomfortable when worn and is somewhat difficult to move 1: It feels very uncomfortable to wear and is difficult to move.

[0078] (Skin adhesion test) The organic electroluminescent sheet was attached to the skin and within one hour, the presence or absence and the degree of peeling were confirmed by visual observation, and the adhesion to the skin and peeling resistance were evaluated as an index of conformability according to the following criteria. The average evaluation results by 10 subjects are shown in Table 2. [Evaluation Criteria] 5: Adhered to the skin, no peeling or lifting was observed with the naked eye 4: Peeling was visually observed, and the area of ​​peeled parts was less than 5%. 3: Peeling was visually observed, and the area of ​​the peeled portion was 5% or more but less than 10%. 2: Peeling was visually observed, and the area of ​​the peeled portion was 10% or more but less than 20%. 1: Peeling and peeling are frequently observed visually, and adhesion is poor.

[0079] [Table 2]

[0080] As shown in Table 2, the organic electroluminescent sheet of the present embodiment has good conformability and adhesion to the skin, reduces discomfort when worn, and is suitable, for example, for long-term use.

[0081] 5. Evaluation of the effect of light irradiation from organic electroluminescence devices on gene expression Using element 1 prepared in Example 1, the following in vitro usefulness evaluation test (gene expression evaluation test using epidermal cells) was carried out in order to evaluate the effect of the element on the expression of various genes by a DNA microarray method using normal human epidermal cells. The RNA concentration and RIN value results recovered from normal human epidermal cells treated with each test sample are shown in Table 3, and the microarray analysis results are shown in Tables 4 and 5. <Test Method> Normal human epidermal cells were cultured in HuMedia-KG2 medium at 2.5 × 10 5 After culturing for 24 hours, all the media were diluted with Hanks buffer (CaCl2+). 2+ ,Mg 2+ The light emitted from the organic electroluminescent device was 2.5 mW / cm 2 of light for 60 minutes at 5mW / cm 2 of light for 30 minutes at 1mW / cm 2 The cells were then exposed to light for 60 minutes. The unexposed area was shielded from light with aluminum foil. After exposure, the medium was replaced with HuMedia-KB2 and cultured for 24 hours. After 24 hours, the cells were stained with QIAzol (R) Dissolve in the reagent. (R) The purified RNA was collected using the QIAGEN Mini Kit. The collected RNA was analyzed using an mRNA expression analysis chip (Genopal DNA chip). (R) DNA microarrays are performed using NDR custom chips. The results are analyzed, and the results of various gene expression analyses are expressed as ratios with the corrected value of the untreated control of the test sample set at 1, and a significant difference test is performed. [Exam details] The number of tests will be n=3. Three 12-well plates are used for the test. Each plate is divided into two sections: "unexposed" and "exposed at 2.5 mW / cm irradiance." 2 , irradiation time 60 minutes, irradiance 5mW / cm 2 , irradiation time 30 minutes, irradiance 1mW / cm 2 There will be four groups: "no exposure time," "60 minutes," and "no exposure time," and the test will be conducted by repeating these three sets. The time that the cells are immersed in Hanks buffer should be the same for both the unexposed and exposed sections. Irradiation is performed by placing a light source on the lid of the 12-well plate.

[0082] [Table 3]

[0083] From Table 3, it was confirmed that the recovered RNA concentration was the same regardless of whether or not light was irradiated, and that the RIN value (0: significant RNA degradation to 10: no degradation) remained high.

[0084] [Table 4]

[0085] [Table 5]

[0086] As can be seen from Tables 4 and 5, the microarray results confirmed that the expression of many genes was suppressed under all three light irradiation conditions. Since no significant changes in the amount of RNA recovered or the RIN value were observed after light irradiation, it is believed that light irradiation does not induce cell damage accompanied by RNA degradation. This suggests that light irradiation under the present conditions may suppress gene expression. Furthermore, under conditions that are not thought to induce cell damage, gene expression of inflammatory factors, factors that induce pigmentation, matrix-degrading enzymes, etc. was reduced, suggesting that light exposure may have an anti-inflammatory effect.

Claims

1. An organic electroluminescent sheet for use in photocosmetic or phototherapy applications, The organic electroluminescent sheet has a structure in which a plurality of layers, including a structure in which a metal oxide layer (excluding conductive metal oxide) and a metal simple substance layer are adjacently laminated on a sheet-like flexible substrate in which the surface of a resin material is coated with an epoxy resin, are laminated, and is composed of an organic electroluminescent element having a thickness of 10 to 100 μm.

1. An organic electroluminescent sheet for photocosmetic or phototherapy.

2. 2. The organic electroluminescent sheet for photocosmetic or phototherapy according to claim 1, wherein the organic electroluminescent element has a cathode made of silver on a metal oxide layer formed on a sheet-like flexible substrate.

3. 3. The organic electroluminescent sheet for photocosmetic or phototherapy according to claim 1, further comprising a thin-film battery.

4. 4. The organic electroluminescent sheet for photocosmetic or phototherapy according to claim 1, wherein the organic electroluminescent sheet has a thickness of 650 μm or less.

5. 5. A photocosmetic device comprising the organic electroluminescent sheet for photocosmetic or phototherapy according to claim 1.

6. A phototherapy device comprising the organic electroluminescent sheet for photocosmetic or phototherapy according to any one of claims 1 to 4.

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