Europium complex-containing cell activation composition

Abstract

To provide a cell activation composition that exhibits superior cell activation capability and has design properties suitable for product application.SOLUTION: A europium complex-containing cell activation composition comprising at least one selected from the group consisting of a resin material, an inorganic glass, a liquid material, and an organic low-molecular material, and a europium complex having a molar extinction coefficient of 10000 L mol-1 cm-1 or more at a wavelength of 350 nm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a cell-stimulating composition containing a europium complex. [Background technology]

[0002] Wavelength converting materials are materials that absorb light of a specific wavelength and emit light at a different wavelength. In recent years, it has been reported that using such wavelength converting materials to convert ultraviolet light in sunlight into visible light has a beneficial effect on the skin. For example, Patent Document 1 discloses a method for activating skin cells by converting ultraviolet light into light of a specific wavelength range using an organic fluorescent substance derived from natural products such as phycocyanin or an inorganic fluorescent substance such as a zinc oxide fluorescent substance. Red light (600 to 700 nm) is known to be particularly effective as a wavelength that has a beneficial effect on skin cells (see, for example, Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020-202764 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-011296 [Patent Document 3] Patent Publication No. 2021-194341 Summary of the Invention [Problem to be solved by the invention]

[0004] In conventional methods of converting ultraviolet light using a wavelength converting material and irradiating the converted light onto skin, the wavelength converting material itself is colored because it also absorbs light in the visible light region. However, when applied to products such as sunscreens, window materials, and eyeglass lenses, coloring the wavelength converting material itself is undesirable from the standpoints of design and color vision, and the wavelength converting materials used in conventional methods of activating skin cells are therefore unsuitable for product application.

[0005] An object of the present disclosure is to provide a cell-activating composition that has excellent cell-activating ability and has design properties suitable for product application. [Means for solving the problem]

[0006] The present inventors have conducted studies focusing on the composition and color tone of wavelength converting materials and compositions containing the same that can be applied to activating skin cells, and have found that a europium complex-containing composition having specific light absorption and emission capabilities is effective as a cell activator without being colored.

[0007] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows. [1] One or more materials selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials, and a molar absorption coefficient at a wavelength of 350 nm of 10,000 L·mol -1 ·cm -1 A europium complex-containing cell stimulating composition comprising the above europium complex. [2] The europium complex-containing cell stimulating composition according to the above [1], wherein the europium complex is a europium complex represented by general formula (1):

[0008] [ka]

[0009] {HC is a ligand represented by general formula (1dk), general formula (1qu), or general formula (1cu).

[0010] [ka]

[0011] [In the formula, each V independently represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a hydrogen atom, an aryl group having 6 to 22 carbon atoms, or a thienyl group.]

[0012] [ka]

[0013] [In the formula, R A represents a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 22 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R B1 , R B2 , R B3 , R B4 and R B5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Also, R B1 , R B2 , R B3 and R B4 Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring.

[0014] [ka]

[0015] [In the formula, R A is R in general formula (1qu) A It has the same meaning as: R C1 , R C2 , R C3 and R C4 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. In addition, the substituent R C1 , R C2 , R C3 and R C4 Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring. n represents 1, 2 or 3. When n is 2 or 3, the ligands may be the same or different. L represents a nitrogen-containing ligand having two or more nitrogen atoms having unshared electron pairs or a phosphine oxide ligand. m represents 0, 1 or 2. When m is 2, L may be the same or different.} [3] The europium complex-containing cell-stimulating composition according to [1] or [2] above, wherein n is 3. [4] The europium complex-containing cell-stimulating composition according to [1] above, wherein the europium complex is a europium complex represented by any one of the following formulae (1-1) to (1-63):

[0016] [ka]

[0017] [ka]

[0018] [ka]

[0019] [5] A europium complex-containing cell-stimulating composition according to any one of [1] to [4] above, which comprises europium complex-containing particles containing one or more materials selected from the group consisting of resin materials, inorganic glass, and organic low-molecular-weight materials, and the europium complex, and one or more materials selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials. [6] A body-worn device comprising the europium complex-containing cell-stimulating composition according to any one of [1] to [5]. [7] A structural material comprising the europium complex-containing cell-stimulating composition according to any one of [1] to [6]. [Effects of the Invention]

[0020] The present disclosure makes it possible to provide a cell-activating composition that has excellent cell-activating ability and has design properties suitable for product application. [Brief explanation of the drawings]

[0021] [Figure 1]FIG. 1 is a schematic diagram illustrating one embodiment of a composition of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram illustrating another embodiment of the composition of the present disclosure. [Figure 3] This is the UV-Vis absorption spectrum of the europium complex (Eu(hfa)3(TPPO)2). [Figure 4] 1 shows the UV-Vis absorption spectrum of europium complex (1-10). [Figure 5] 1 shows the UV-Vis absorption spectrum of europium complex (1-32). [Figure 6] This is the UV-Vis absorption spectrum of europium complex (1-61). [Figure 7] UV-Vis absorption spectrum of phycocyanin. [Figure 8] 1 shows the radiation spectrum of the wavelength-converting material-containing film obtained in Comparative Example 1. (The wavy line a is the radiation spectrum without the film, and the solid line b is the radiation spectrum of Comparative Example 1.) [Figure 9] 1 shows the radiation spectrum of the wavelength-converting material-containing film obtained in Example 1. (The wavy line a is the radiation spectrum without the film, and the solid line b is the radiation spectrum of Example 1.) [Figure 10] 1 shows the emission spectrum of the wavelength-converting material-containing film obtained in Example 2. (The wavy line a is the emission spectrum without the film, and the solid line b is the emission spectrum of Example 2.) [Figure 11] 1 shows the emission spectrum of the wavelength-converting material-containing film obtained in Example 3. (The wavy line a is the emission spectrum without the film, and the solid line b is the emission spectrum of Example 3.) [Figure 12] 1 shows the transmission spectrum of the film used in Evaluation Example 3. (The wavy line a is the transmission spectrum of the UV-cut film, and the solid line b is the transmission spectrum of Example 2.) [Figure 13] 1 shows the results of evaluating the cell viability of human epidermal keratinocytes obtained in Evaluation Example 3. (a is the cell viability without a film, b is the cell viability with a UV-cut film, and c is the cell viability in Example 2.) [Figure 14]1 shows the results of evaluating the cell viability of human skin fibroblasts obtained in Evaluation Example 3. (a is the cell viability without a film, b is the cell viability with a UV-cut film, and c is the cell viability in Example 2.) [Figure 15] 1 shows the results of evaluation of the amount of hyaluronic acid produced by human skin fibroblasts obtained in Evaluation Example 4. (a is the amount of hyaluronic acid produced without exposure to artificial sunlight, b is the amount of hyaluronic acid produced when a UV-cut film was used, and c is the amount of hyaluronic acid produced in Example 2.) DETAILED DESCRIPTION OF THE INVENTION

[0022] The present disclosure will be described in detail below. However, the embodiments described below are examples of the present disclosure, and the present disclosure is not limited to these contents. Furthermore, the present disclosure includes any combination of the configurations and parameters disclosed in this specification, and any combination of the upper and lower limits of the values ​​disclosed in this specification is also included in the present disclosure. [Europium complex-containing composition] The present embodiment is directed to a method for manufacturing a liquid crystal display device using a liquid crystal display device, comprising: a liquid crystal display device, ... -1 ·cm -1 The present invention provides a europium complex-containing cell stimulating composition containing the above europium complex.

[0023] The europium complex-containing composition of this embodiment (hereinafter also referred to as the "composition of this embodiment") has a molar absorption coefficient of 10,000 L mol -1 ·cm -1 The present invention also includes a europium complex having a molar absorption coefficient of 10,000 L mol or more (hereinafter also referred to as the "europium complex of the present embodiment"). -1 ·cm -1If the red light is less than 1000 kJ / s, the irradiance of the red light is too low to achieve the skin revitalization effect. The molar extinction coefficient is a value measured based on the Beer-Lambert law, and is measured using a UV-Vis-NIR spectrophotometer (e.g., V-670 manufactured by JASCO Corporation) under the following conditions:

[0024] Data acquisition interval: 1 nm Bandwidth 1.0 nm Scanning speed: 400 nm / min Measurement solvent: chloroform or water The molar extinction coefficient is 15,000 L mol -1 ·cm -1 It is preferable that the value is 25,000 L·mol or more. -1 ·cm -1 The upper limit of the molar extinction coefficient is 1,000,000 L mol -1 ·cm -1 Less than or equal to 5,000,000 L·mol -1 ·cm -1 For example, 15,000 L·mol -1 ·cm -1 More than 1000000L mol -1 ·cm -1 or less, or 25,000 L·mol -1 ·cm -1 More than 5000000L mol -1 ·cm -1 It is preferable that:

[0025] The composition of the present embodiment contains one or more materials (hereinafter also referred to as "medium") selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials, preferably a resin material. The medium may be any material that does not absorb light in the visible light range, and such a material will make the medium itself colorless and transparent.

[0026] The resin materials are polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, fluorine-containing polymethyl methacrylate, fluorine-containing polyethyl methacrylate, fluorine-containing polypropyl methacrylate, fluorine-containing polyisopropyl methacrylate, fluorine-containing polybutyl methacrylate, fluorine-containing polysec-butyl methacrylate, fluorine-containing polyisobutyl methacrylate, fluorine-containing polytert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, polyisobutyl acrylate, polyte Examples include rt-butyl acrylate, fluorine-containing polymethyl acrylate, fluorine-containing polyethyl acrylate, fluorine-containing polypropyl acrylate, fluorine-containing polyisopropyl acrylate, fluorine-containing polybutyl acrylate, fluorine-containing polysec-butyl acrylate, fluorine-containing polyisobutyl acrylate, fluorine-containing polytert-butyl acrylate, polystyrene, polyethylene, polypropylene, polybutene, fluorine-containing polyethylene, fluorine-containing polypropylene, fluorine-containing polybutene, polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, or copolymers thereof; cellulose; polyacetal; polyester; polycarbonate; epoxy resin; urethane resin; thiourethane resin; polyamide resin; polyimide resin; polyurethane; Nafion; petroleum resin; rosin; or silicone resin.Among these, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof; epoxy resins; polyimide resins; and silicone resins are preferred, and polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof; epoxy resins; urethane resins; thiourethane resins; polyimide resins; and silicone resins are more preferred. These may be used alone or in combination of two or more.

[0027] Examples of inorganic glass include soda glass, crystal glass, and borosilicate glass, which may be used alone or in combination of two or more.

[0028] Examples of liquid materials include water, ethanol, glycerin, propylene glycol, isopropyl alcohol, butylene glycol, hexanediol, cetyl ethylhexanoate, decamethylcyclopentasiloxane, glyceryl caprylate, methylpropanediol, ethyl acetate, glycerol, sorbitol, propanediol, isobutane, ethylene glycol, pentanediol, hexanediol, octanediol, decane, and caprylic acid triglyceride. These may be used alone or in combination of two or more.

[0029] Examples of organic low-molecular-weight materials include amyltriethylammonium bis(trifluoromethanesulfonyl)imide, tetraamylammonium chloride, pentadecane, hexadecane, octadecane, nonadecane, icosane, and paraffin. These may be used alone or in combination of two or more.

[0030] The composition of the present embodiment may be in any form, provided that it is at least one of a liquid and a solid. When the medium is a liquid material, the composition of the present embodiment is a liquid. On the other hand, when the medium is one or more selected from the group consisting of a resin material, an inorganic glass, and an organic low-molecular-weight material, the composition of the present embodiment is a solid, such as a lump, pellet, thin film, or powder, with a lump or thin film being preferred.

[0031] The content of the medium in the composition of this embodiment can be, for example, 1% by mass or more, 25% by mass or more, or 50% by mass or more, and can be, for example, 99.99% by mass or less, 99.9% by mass or less, or 99% by mass or less.

[0032] The content of the medium in the composition of this embodiment is the remainder (mass %) obtained by subtracting the content of the europium complex from the content of the europium complex-containing composition.

[0033] The content of the europium complex in the composition of this embodiment can be, for example, 0.01% by mass or more, 1% by mass or more, or 10% by mass or more, and 80% by mass or less, 50% by mass or less, or 20% by mass or less. The content of the europium complex is preferably 0.01% by mass or more and 80% by mass or less, and more preferably 0.1% by mass or more and 50% by mass or less. In this embodiment, the content of the europium complex can be determined by ICP-AES measurement. The ICP-AES measurement is performed using a general ICP-AES device (e.g., 5800 ICP-OES manufactured by Agilent Technologies) to determine the content of europium complex converted into europium complex. The content of the europium complex can be determined by the mass ratio (mass %) of the converted mass of the europium complex to the mass of the europium complex-containing composition.

[0034] The composition of the present embodiment preferably has a composition in which the europium complex and the medium account for 100% by mass, but may contain other components as long as the effect is achieved. The other components may include one or more selected from the group consisting of organic solvents, ligands of the europium complex, and additives contained in the medium, as well as other components derived from the synthesis of the europium complex.

[0035] The composition of this embodiment may be a composition comprising a europium complex and a medium. FIG. 1 is a schematic diagram conceptually illustrating the structure of the composition of this embodiment. In FIG. 1, 11 represents a medium, 10 represents a europium complex, and 100 represents a composition having a structure in which a europium complex is contained in a medium. In FIG. 1, the europium complexes are individually and independently contained in the medium, but the europium complexes may also be contained in the medium in a partially aggregated state. When the medium is a resin material, a liquid material, or an organic low-molecular-weight material, the composition has a structure in which the europium complex is dissolved or dispersed in the medium. When the medium is inorganic glass, the composition has a structure in which the europium complex is aggregated or dispersed in the inorganic glass.

[0036] The composition of this embodiment may be a composition comprising europium-complex-containing particles made of one or more materials (hereinafter also referred to as "matrix") selected from the group consisting of resin materials, inorganic glass, and organic low-molecular-weight materials, and one or more materials (medium) selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials containing the particles. FIG. 2 is a schematic diagram conceptually illustrating the structure of a composition of this embodiment, comprising europium-complex-containing particles made of a matrix and a medium containing the particles. In FIG. 2, 21 represents the medium, 20 represents the europium complex, and 22 represents the matrix, and 200 represents a composition having a structure in which europium-complex-containing particles are contained in the medium. In FIG. 2, the europium-complex-containing particles are shown to contain multiple europium complexes, but the amount of europium complex contained in the europium-complex-containing particles is arbitrary. Furthermore, the number of europium complexes contained in the europium-complex-containing particles may be the same or different. The medium and the matrix are preferably made of a resin material, and the composition has a structure in which europium complex-containing particles are contained in a medium made of a resin material. The medium and the matrix may be the same or different.

[0037] The state of the europium complex in the composition of this embodiment may be any state, as long as the europium complex is dissolved, aggregated, or dispersed in the medium, and is preferably dissolved or dispersed. The state of the europium complex in the composition of this embodiment may be observed by SEM-EDS analysis or EPMA analysis. The analysis may be performed based on the mapping results of europium element measured using a general SEM-EDS device (e.g., JSM-IT500, manufactured by JEOL Ltd.) or EPMA device (e.g., EPMA610, manufactured by Shimadzu Corporation). When the medium and the matrix are the same, EPMA analysis detects europium from the europium-complex-containing particles along the particle shape, but does not detect europium from the medium, making it possible to distinguish the boundary between the europium-complex-containing particles and the medium. [Europium complex] The europium complex contained in the composition of the present embodiment is preferably a europium complex represented by general formula (1) (hereinafter also referred to as "europium complex (1)").

[0038] [ka]

[0039] {HC is a ligand represented by general formula (1dk), general formula (1qu), or general formula (1cu).

[0040] [ka]

[0041] In the formula, each V independently represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a hydrogen atom, an aryl group having 6 to 22 carbon atoms, or a thienyl group.

[0042] [ka]

[0043] [In the formula, R A represents a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 22 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. Substituent R B1 , R B2 , R B3 and R B4 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R B5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 22 carbon atoms. In addition, the substituent R B1 , R B2 , R B3 and R B4Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring.

[0044] [ka]

[0045] [In the formula, R A is R in general formula (1qu) A It has the same meaning as: R C1 , R C2 , R C3 and R C4 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In addition, the substituent R C1 , R C2 , R C3 and R C4 Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring. n represents 1, 2 or 3. When n is 2 or 3, the ligands may be the same or different. L represents a nitrogen-containing ligand having two or more nitrogen atoms having unshared electron pairs or a phosphine oxide ligand. m represents 0, 1 or 2. When m is 2, L may be the same or different.} Each of the substituents in the europium complex (1) will be explained below. In this specification, the term "hydrogen atom" includes deuterium and tritium atoms.

[0046] (About V) The alkyl group having 1 to 6 carbon atoms represented by V may be either a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-(1,1-dimethylethyl) group, a pentyl group, a 2-methylpentyl group, a 1-methylbutyl group, a 1,2-dimethylbutyl group, and a 1-ethylpropyl group. The 1-(1,1-dimethylethyl) group is preferred because of its inexpensive raw material.

[0047] The fluoroalkyl group having 1 to 6 carbon atoms represented by V may be either a linear or branched fluoroalkyl group, and specific examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoropropan-2-yl group, a 2,2,2 -trifluoro-1-(trifluoromethyl)ethyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,1,1,2,3,3,4,4,4-nonaorobutan-2-yl group, 1,1,1-trifluorobutan-2-yl group, 4,4,4-trifluorobutan-2-yl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4 ,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, perfluoropentan-2-yl group, 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentan-2-yl group, 1,1,2,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butyl group, 1,1,2,2,3,4,4,4-octafluoro-3-(trifluoromethyl)butyl group, 1,1,3,3,3-pentafluoro-2,2-bis(trifluoromethyl)propyl group, 1,1,1,2,3,3,4,4 ,4-nonafluoro-1-(trifluoromethyl)butan-2-yl group, perfluorohexyl group, 1,1,1,2,3,3,4,4,5,5,6,6,6-decafluorohexan-2-yl group, 1,1,2,3,3,4,4,5,5,5,5-decafluoro-2-(trifluoromethyl)pentyl group, 1,1,2,2,3,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pentyl group, 1,1,2,2,3,3,4,5,5,5-decafluoro-4-(trifluoromethyl)pentyl group, 1,1,1,2,2,3,3,4,4,5,5,Examples include 5-dodecafluoro-1-(trifluoromethyl)pentan-2-yl group, 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentan-2-yl group, 1,1,1,2,2,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pentan-2-yl group, 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl group, 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, and 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group. In terms of readily available raw materials, trifluoromethyl group, 2,2,2-trifluoroethyl group, and perfluoropropyl group are preferred, and in terms of inexpensive raw materials, trifluoromethyl group is more preferred.

[0048] Specific examples of the aryl group having 6 to 22 carbon atoms represented by V include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,5-trimethylphenyl group, a 2,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2 ... Methylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group Examples of the alkyl group include a 2-methylphenyl group, a 2-propylphenyl group, a 3-propylphenyl group, a 4-propylphenyl group, a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, a 2-cyclopropylphenyl group, a 3-cyclopropylphenyl group, a 4-cyclopropylphenyl group, a 2-butylphenyl group, a 3-butylphenyl group, a 4-butylphenyl group, a 2-(1-methylpropyl)phenyl group, a 3-(1-methylpropyl)phenyl group, a 4-(1-methylpropyl)phenyl group, a 2-(2-methylpropyl)phenyl group, a 3-(2-methylpropyl)phenyl group, a 4-(2-methylpropyl)phenyl group, a 2-cyclobutylphenyl group, a 3-cyclobutylphenyl group, a 4-cyclobutylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 9-anthryl group, a 2-phenanthrenyl group, a 3-phenanthrenyl group, and a 9-phenanthrenyl group. A phenyl group, a 2-naphthyl group, or a 2-biphenylyl group is preferred in that the raw materials are readily available, and a phenyl group is more preferred in that the raw materials are inexpensive.

[0049] Specific examples of the thienyl group represented by V include a 2-thienyl group, a 3-thienyl group, a 2-benzothienyl group, a 3-benzothienyl group, and a 2-(trifluoromethyl)-3-thienyl group. The 2-thienyl group is preferred because the raw material is inexpensive.

[0050] (R A About R A Examples of the fluoroalkyl group having 1 to 6 carbon atoms and represented by the formula (I) include the substituents exemplified as the fluoroalkyl group having 1 to 6 carbon atoms and represented by V. In view of the ease of availability of raw materials, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a 2,2,2-trifluoroethyl group, or a perfluoropropyl group is preferred, and in view of the inexpensiveness of the raw material, a trifluoromethyl group is more preferred.

[0051] R ASpecific examples of the heteroaryl group having 3 to 20 carbon atoms represented by the formula (I) include a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-pyrrolyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a 1-methylpyrrol-2-yl group, a 1-methylpyrrol-3-yl group, a 1-phenylpyrrol-2-yl group, a 1-phenylpyrrol-3-yl group, a 2-benzofuranyl group, a 3-benzofuranyl group, a 2-benzothienyl group, a 3-benzothienyl group, a 1-indolyl group, a 2-indolyl group, a 3-indolyl group, a 1-methylindol-2-yl group, a 1-methylindol-2-yl group, a 1-methylindol-3 ... Chilindol-3-yl group, 1-phenylindol-2-yl group, 1-phenylindol-3-yl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-ethylcarbazol-2-yl group, 9-ethylcarbazol-3-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, dibenzofuran-4-yl group, dibenzothiophen-2-yl group, dibenzothiophen-3-yl group, dibenzothiophen-4-yl group yl group, 5-(trifluoromethyl)furan-2-yl group, 2-(trifluoromethyl)furan-3-yl group, 5-(trifluoromethyl)thiophen-2-yl group, 2-(trifluoromethyl)-3-thienyl group, 5-(trifluoromethyl)benzofuran-2-yl group, 6-(trifluoromethyl)benzofuran-2-yl group, 5-(trifluoromethyl)benzothiophen-2-yl group, 6-(trifluoromethyl)benzothiophen-2-yl group, 9-methyl-5-(trifluoromethyl)carbazol-2-yl group, 9-methyl-6-( (trifluoromethyl)carbazol-2-yl group, 9-methyl-5-(trifluoromethyl)carbazol-3-yl group, 9-methyl-6-(trifluoromethyl)carbazol-3-yl group, 9-phenyl-5-(trifluoromethyl)carbazol-2-yl group, 9-phenyl-5-(trifluoromethyl)carbazol-3-yl group, 9-phenyl-6-(trifluoromethyl)carbazol-2-yl group, 9-phenyl-6-(trifluoromethyl)carbazol-3-yl group, 6-(trifluoromethyl)dibenzofuran-2-yl group,Examples include a 7-(trifluoromethyl)dibenzofuran-2-yl group, a 6-(trifluoromethyl)dibenzofuran-3-yl group, a 7-(trifluoromethyl)dibenzofuran-3-yl group, a 6-(trifluoromethyl)dibenzofuran-4-yl group, a 7-(trifluoromethyl)dibenzofuran-4-yl group, a 6-(trifluoromethyl)dibenzothiophen-2-yl group, a 7-(trifluoromethyl)dibenzothiophen-2-yl group, a 6-(trifluoromethyl)dibenzothiophen-3-yl group, a 7-(trifluoromethyl)dibenzothiophen-3-yl group, a 6-(trifluoromethyl)dibenzothiophen-4-yl group, or a 7-(trifluoromethyl)dibenzothiophen-4-yl group. In view of ease of synthesis, a 2-furanyl group, a 2-thienyl group, a 2-benzofuranyl group, a 2-benzothienyl group, a 9-methylcarbazol-3-yl group, a 9-ethylcarbazol-3-yl group, a 9-phenylcarbazol-3-yl group, a dibenzofuran-2-yl group, a dibenzofuran-3-yl group, a dibenzofuran-4-yl group, a dibenzothiophen-2-yl group, a dibenzothiophen-3-yl group, a dibenzothiophen-4-yl group, a 5-(trifluoromethyl)furan-2-yl group, or a 5-(trifluoromethyl)thiophen-2-yl group is preferred, and in view of inexpensive raw materials, a 2-furanyl group, a 2-thienyl group, a 2-benzofuranyl group, or a 2-benzothienyl group is more preferred.

[0052] (R B1 , R B2 , R B3 , R B4 and R B5 About R B1 , R B2 , R B3 , R B4 and R B5The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be either a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-(1,1-dimethylethyl) group, a pentyl group, a 2-methylpentyl group, a 1-methylbutyl group, a 1,2-dimethylbutyl group, and a 1-ethylpropyl group. A methyl group is preferred from the viewpoint of ease of synthesis.

[0053] R B1 , R B2 , R B3 , R B4 and R B5 Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by the formula (I) include a 3-cyclopropylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, a bicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-2-yl group, an adamantan-2-yl group, a bicyclo[2.2.1]heptan-2-yl group, and an adamantan-1-yl group. A cyclohexyl group is preferred from the viewpoint of ease of synthesis.

[0054] R B5Specific examples of the aryl group having 6 to 22 carbon atoms represented by the formula (I) include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,5-trimethylphenyl group, a 2,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2 ... Methylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group Examples of the alkyl group include a 2-methylphenyl group, a 2-propylphenyl group, a 3-propylphenyl group, a 4-propylphenyl group, a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, a 2-cyclopropylphenyl group, a 3-cyclopropylphenyl group, a 4-cyclopropylphenyl group, a 2-butylphenyl group, a 3-butylphenyl group, a 4-butylphenyl group, a 2-(1-methylpropyl)phenyl group, a 3-(1-methylpropyl)phenyl group, a 4-(1-methylpropyl)phenyl group, a 2-(2-methylpropyl)phenyl group, a 3-(2-methylpropyl)phenyl group, a 4-(2-methylpropyl)phenyl group, a 2-cyclobutylphenyl group, a 3-cyclobutylphenyl group, a 4-cyclobutylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 9-anthryl group, a 2-phenanthrenyl group, a 3-phenanthrenyl group, and a 9-phenanthrenyl group. A phenyl group, a 2-naphthyl group, or a 2-biphenylyl group is preferred in that the raw materials are readily available, and a phenyl group is more preferred in that the raw materials are inexpensive.

[0055] R B1 , R B2 , R B3 and RB4 Among these, two adjacent substituents (e.g., R 2 and R 3 ) may form a 5-membered ring, a 6-membered ring, or a 7-membered ring together with the benzene ring to which it is bonded, and examples of the structure of the quinolinonato ligand (1qu) include the following structures represented by (1qu-1), (1qu-2), and (1qu-3).

[0056] [ka]

[0057] (In the formula, R B6 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R B1 , R B2 , R B3 , R B4 and R B6 is preferably a hydrogen atom in that the raw materials are readily available.

[0058] R B5 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group or a 2-biphenylyl group in terms of easy availability of raw materials.

[0059] (R C1 , R C2 , R C3 and R C4 About R C1 , R C2 , R C3 and R C4 As the alkyl group having 1 to 10 carbon atoms represented by the formula B1 , R B2 , R B3 , R B4 and R B5 Examples include alkyl groups having 1 to 10 carbon atoms as exemplified in the above. A methyl group is preferred in terms of ease of synthesis.

[0060] R C1 , R C2 , R C3 and RC4 Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by the formula: B1 , R B2 , R B3 , R B4 and R B5 Examples include cycloalkyl groups having 3 to 10 carbon atoms as exemplified in the following. A cyclohexyl group is preferred from the viewpoint of ease of synthesis.

[0061] R C1 , R C2 , R C3 and R C4 Among these, two adjacent substituents may be bonded to the benzene ring to form a 5-membered ring, a 6-membered ring, or a 7-membered ring together. For example, examples of the structure of the coumarinato ligand (1cu) include the following structures (1cu-1), (1cu-2), and (1cu-3).

[0062] [ka]

[0063] (In the formula, R C5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R C1 , R C2 , R C3 , R C4 and R C5 is preferably a hydrogen atom in that the raw materials are readily available. (About L) Examples of nitrogen-containing ligands having two or more nitrogen atoms with unshared electron pairs include 1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,4,7,9-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 5-chloro- chloro-1,10-phenanthroline, 2-chloro-1,10-phenanthroline, 2,9-dichloro-1,10-phenanthroline, 4,7-dichloro-1,10-phenanthroline, 5-bromo-1,10-phenanthroline, 2-bromo-1,10-phenanthroline, 3-bromo-1,10-phenanthroline, 3,8-dibromo-1,10-phenanthroline, 4,7-dibromo-1,10-phenanthroline, 3,5,6,8-tetrabromo-1,10-phenanthroline, 5-hydroxy-1,10-phenanthroline, 4,7-dihydroxy si-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 5-amino-1,10-phenanthroline, 5,6-diamino-1,10-phenanthroline, 5-nitro-1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, 2,2'-bipyridine, 2,2'-bipyridine-d8, 2,2'-bipyridine-6-carbonitrile, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2, 2'-Bipyridine, 4,4'-diamino-2,2'-bipyridine, 2,2'-bipyridyl-1,1'-dioxide, 2,2'-bipyridine-5,5'-diol, 6,6'-dicyano-2,2'-bipyridine, 4,4'-bis(dihydroxymethyl)-2,2'-bipyridine, 4,4'-dinonyl-2,2'-bipyridine, 4,4'-di(tert-butyl)-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 2,2':6'2''-terpyridine, 6-bromo-2,2'-bipyridine, 4-bromo-2,2'-bipyridine, 4,4'-dibromo-2,2'-bipyridine, 5,5'-dibromo-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4',5,5'-tetramethyl-2,2'-bipyridine, 4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine, 4,4'-bis(dimethylamino)-2,2'-bipyridine, 4,4'-difluoro-2,2'-bipyridine, 5,5'-difluoro-2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine, 5,5'-bis(trifluoromethyl)-2,2'-bipyridine, Examples include dimethyl-2,2'-bipyridine-4,4'-dicarboxylate, dimethyl-2,2'-bipyridine-5,5'-dicarboxylate, diethyl-2,2'-bipyridine-4,4'-dicarboxylate, diethyl-2,2'-bipyridine-5,5'-dicarboxylate, dipyrido[3,2-a:2',3'-c]phenazine, 2,2'-biquinoline, 4,5-diazafluoren-9-one; N,N-diethyl-4-{[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazin-2-yl]}aniline, and 2,2'-bipyridine or phenanthroline is preferred.

[0064] Examples of the structure of the phosphine oxide ligand include structures represented by any of the following (3a-1) to (3a-16) and (3b-1) to (3a-13).

[0065] [ka]

[0066] [ka]

[0067] In view of the ease of availability of raw materials, the phosphine oxide ligand is preferably (3a-1), (3a-6), (3a-8) or (3a-9).

[0068] Specific examples of the europium complex (1) include europium complexes represented by any one selected from the group consisting of formulas (1-1) to (1-63).

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] Among the compounds represented by formulas (1-1) to (1-63), one or more selected from the group of compounds represented by formulas (1-1) to (1-5), (1-7), (1-13), (1-25) to (1-39), and (1-49) to (1-63) are preferred in terms of excellent solubility in solvents and resins, and one or more selected from the group of compounds represented by formulas (1-1), (1-7), (1-13), (1-31), (1-32), (1-37), (1-38), (1-49), (1-50), (1-55), (1-56), (1-61), and (1-62) are more preferred in terms of inexpensive raw materials. [Method for producing europium complexes] The europium complex (1) may be produced by any method, but the preferred method is as follows: An example of a production method is a method comprising reacting an enol (hereinafter also referred to as "enol (4)") represented by one or more selected from the group consisting of the following general formulae (4dk), (4qu), and (4cu), with a neutral ligand selected from the group consisting of nitrogen-containing ligands having two or more nitrogen atoms with unshared electron pairs, represented by L, or phosphine oxide ligands (3), with a europium compound.

[0073] [ka]

[0074] (In the formula, L has the same meaning as L in general formula (1)).

[0075] [ka]

[0076] (wherein V has the same meaning as V in general formula (1)).

[0077] [ka]

[0078] (R in the formula A , R B1 , R B2 , R B3 、 R B4 and R B5 is R in general formula (1) A , R B1 , R B2 , R B3 、 R B4 and R B5 It has the same meaning as

[0079] [ka]

[0080] (In the formula, R A , R C1 , R C2 , R C3 and R C4 is R in general formula (1) A , R C1 , R C2 , R C3 and R C4 means the same thing.)

[0081] V, R A , R B1 , R B2 , R B3、 R B4 , R B5 , R C1 , R C2 , R C3 、 R C4 The definitions and specific examples of V, R and L in the general formula (1) are the same as those in the general formula (1). A , R B1 , R B2 , R B3 、 R B4 , R B5 , R C1 , R C2 , R C3 、 R C4 and L.

[0082] L can be obtained by the method described in Chemical Reviews, Vol. 60, pp. 243-260, 1960, or the like.

[0083] Enol (4) can be obtained, for example, by the method described in The Journal of Organic Chemistry, Vol. 75, pp. 2741-2744, 2010; Journal of the American Chemical Society, Vol. 66, pp. 1220-1222, 1944; Tetrahedron, Vol. 74, pp. 2762-2768, 2018; The Journal of Organic Chemistry, Vol. 80, pp. 10643-10650, 2015.

[0084] Enol (4) may be at least one of an enol that loses an active proton when treated with a base to form an organic salt and its organic salt. Specific examples of the counter cation of the organic salt include lithium ion, sodium ion, potassium ion, cesium ion, triethylammonium ion, trimethylammonium ion, diisopropylethylammonium ion, diethylammonium ion, diisopropylammonium ion, pyridinium ion, 2,6-dimethylpyridinium ion, imidazolium ion, N-methylimidazolium ion, and ammonium ion.

[0085] The europium compound may be any compound containing europium (Eu), and examples thereof include europium (III) fluoride, europium (III) chloride, europium (III) bromide, europium (III) iodide, europium (III) fluoride hydrate, europium (III) chloride hydrate, europium (III) bromide hydrate, europium (III) iodide hydrate, europium (III) oxalate, europium (III) acetate, europium (III) trifluoroacetate, europium (III) trifluoromethanesulfonate, europium (III) oxalate hydrate, europium (II) acetate, and europium(III) phosphate, europium(III) sulfate, europium(III) nitrate, europium(III) phosphate hydrate, europium(III) sulfate hydrate, and europium(III) nitrate hydrate. In terms of good reaction yield, the europium compound is preferably europium(III) chloride, europium(III) nitrate, europium(III) chloride hydrate, europium(III) nitrate hydrate, europium(III) oxalate, europium(III) acetate, europium(III) trifluoroacetate, europium(III) trifluoromethanesulfonate, europium(III) oxalate hydrate, europium(III) acetate hydrate, europium(III) trifluoroacetate hydrate, or europium(III) trifluoromethanesulfonate hydrate, and more preferably europium(III) acetate, europium(III) chloride, europium(III) nitrate, europium(III) acetate hydrate, europium(III) chloride hydrate, or europium(III) nitrate hydrate.

[0086] The use of a solvent is preferred because it improves the yield of europium complex (1). The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples of solvents include dichloromethane, chloroform, chlorobenzene, methanol, ethanol, propanol, isopropyl alcohol, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, tetrahydrofuran, cyclopentyl methyl ether, tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, acetone, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, xylene, and water. These solvents can be used alone or in combination of two or more in any ratio. The solvent is preferably one or more selected from the group consisting of chloroform, methylcyclohexane, acetone, methanol, ethanol, toluene and water, in terms of a good reaction yield of the resulting europium complex (1).

[0087] It is preferable to use 1.0 to 5.0 moles of enol (4) per 1.0 mole of europium compound, and more preferably 3.0 to 4.0 moles of enol (4).

[0088] It is preferable to use L in an amount of 0.25 moles or more and 2.5 moles or less, and more preferable to use L in an amount of 0.5 moles or more and 1.5 moles or less, per 1.0 mole of the europium compound.

[0089] It is preferable to use L in an amount of 0.5 to 5.0 moles, more preferably 1.0 to 3.0 moles, per 1.0 mole of the europium compound.

[0090] A base may be added to promote the reaction. Examples of the base include one or more selected from the group consisting of trimethylamine, triethylamine, diethylamine, pyridine, sodium quinoline carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide. The equivalent amount of the base is preferably 1.0 to 10 moles, more preferably 2.0 to 8.0 moles, and even more preferably 3.0 to 5.0 moles, per 1.0 mole of enol (4).

[0091] The reaction temperature and reaction time are not particularly limited, and general conditions used by those skilled in the art when producing metal complexes can be used. Specific examples include a reaction temperature of -80°C or higher and 120°C or lower, and a reaction time of 1 minute or higher and 120 hours or shorter.

[0092] The produced europium complex (1) can be purified by a purification method generally used by those skilled in the art for purifying metal complexes, which may include one or more methods selected from the group consisting of filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, precipitation, and column chromatography. [Method for producing europium complex-containing composition] The composition of this embodiment may be produced by any method as long as it satisfies the above-mentioned requirements. A preferred production method is a method for producing a europium complex-containing composition by mixing a europium complex (1) with one or more materials selected from the group consisting of a resin material, an inorganic glass, a liquid material, and an organic low-molecular-weight material.

[0093] The mixing may be carried out so that the amount of the europium complex is 0.01% by mass or more, 1% by mass or more, or 10% by mass or more relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex (1). The amount of the europium complex is 20% by mass or less, 50% by mass or less, or 80% by mass or less relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex (1). It is also preferable that the amount of the europium complex is 0.01% by mass or more and 80% by mass or less, or 1% by mass or more and 50% by mass or less relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex (1).

[0094] The mixing method may be one or more selected from the group consisting of mechanical stirring, ultrasonic homogenizer mixing, mechanical mixing, and co-evaporation.

[0095] In the production method of this embodiment, the europium complex-containing composition obtained by mixing may be further molded by one or more molding methods selected from the group consisting of injection molding, blow molding, extrusion molding, T-die molding, inflation molding, vacuum molding, pressure molding, calendar molding, press molding, and sol-gel coating.

[0096] When the composition of the present embodiment comprises one or more (matrix) selected from the group consisting of resin materials, inorganic glass, and organic low-molecular-weight materials, europium-complex-containing particles containing a europium complex, and one or more (medium) selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials, a preferred production method is a method for producing a europium-complex-containing composition by mixing one or more (matrix) selected from the group consisting of resin materials, inorganic glass, and organic low-molecular-weight materials, europium-complex-containing particles containing a europium complex, and one or more (medium) selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials.

[0097] The mixing may be carried out so that the amount of europium complex-containing particles is 0.01% by mass or more, 1% by mass or more, or 10% by mass or more relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex-containing particles. The amount of europium complex-containing particles is 20% by mass or less, 50% by mass or less, or 80% by mass or less relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex-containing particles. It is also preferred that the amount of europium complex-containing particles is 0.01% by mass or more and 80% by mass or less, or 1% by mass or more and 50% by mass or less relative to the total mass of the resin material, inorganic glass, liquid material, organic low-molecular-weight material, and europium complex-containing particles.

[0098] The mixing method may be one or more selected from the group consisting of mechanical stirring, ultrasonic homogenizer mixing, mechanical mixing, and co-evaporation.

[0099] The europium complex-containing composition obtained by mixing may be further molded by one or more molding methods selected from the group consisting of injection molding, blow molding, extrusion molding, T-die molding, inflation molding, vacuum molding, pressure molding, calendar molding, press molding, and sol-gel coating, with extrusion molding being preferred. [Method for producing europium complex-containing particles] The europium-complex-containing particles may be produced by any method as long as they satisfy the above-mentioned requirements. A preferred production method, when the matrix is ​​a resin material, includes a polymerization step of mixing a monomer and a europium complex, and then polymerizing the europium-complex-containing monomer to obtain europium-complex-containing particles.

[0100] In the polymerization step, a monomer and a europium complex are mixed, and then the monomer is polymerized to obtain europium complex-containing particles. One method for mixing the monomer and the europium complex is to add the europium complex to the liquid monomer and dissolve the europium complex in the monomer by stirring.

[0101] The polymerization method is not particularly limited as long as it is a known method, and examples thereof include suspension polymerization and emulsion polymerization. Suspension polymerization is a preferred polymerization method because it has advantages such as easy reaction control. In suspension polymerization, the above-mentioned monomer is polymerized in a solvent in the presence of a polymerization initiator soluble in the monomer. As the polymerization initiator, for example, a radical polymerization initiator can be used. As the radical polymerization initiator, there is no particular limitation, but examples thereof include peroxides, and for example, at least one of an organic peroxide and an azo-based initiator can be used.

[0102] The amount of the monomer mixed, relative to the total mass of the monomer and the europium complex, can be, for example, 1% by mass or more, 25% by mass or more, or 50% by mass or more, and can be, for example, 99.999% by mass or less, 99.99% by mass or less, or 99.9% by mass or less, and examples thereof include 1% by mass or more and 99.999% by mass or less, or 50% by mass or more and 99.9% by mass or less.

[0103] The amount of the europium complex mixed, relative to the total mass of the monomer and the europium complex, can be, for example, 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, and can be, for example, 99% by mass or less, 75% by mass or less, or 50% by mass or less, and can be 0.001% by mass or more and 99% by mass or less, or 0.1% by mass or more and 50% by mass or less.

[0104] Examples of the monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, fluorine-containing methyl methacrylate, fluorine-containing ethyl methacrylate, fluorine-containing propyl methacrylate, fluorine-containing isopropyl methacrylate, fluorine-containing butyl methacrylate, fluorine-containing sec-butyl methacrylate, fluorine-containing isobutyl methacrylate, fluorine-containing tert-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, Examples of the methyl acrylate include at least one selected from the group consisting of methyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, fluorine-containing methyl acrylate, fluorine-containing ethyl acrylate, fluorine-containing propyl acrylate, fluorine-containing isopropyl acrylate, fluorine-containing butyl acrylate, fluorine-containing sec-butyl acrylate, fluorine-containing isobutyl acrylate, fluorine-containing tert-butyl acrylate, styrene, ethylene, propylene, butene, fluorine-containing ethylene, fluorine-containing propylene, fluorine-containing butene, vinyl ether, fluorine-containing vinyl ether, vinyl acetate, and vinyl chloride, and methyl methacrylate and styrene are preferred.

[0105] Examples of the organic peroxide include one or more selected from the group consisting of benzoyl peroxide, isobutyl peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, and diisopropylbenzene hydroperoxide.

[0106] Examples of the azo initiator include one or more selected from the group consisting of 2,2'-azobisisobutyronitrile (azoisobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobisisobutyrate.

[0107] The amount of polymerization initiator added is not particularly limited, but examples thereof include 0.01% by mass or more, or 0.1% by mass or more, and 5% by mass or less, or 2.5% by mass or less, relative to 100% by mass of the monomer, and examples thereof include 0.01% by mass or more and 5% by mass or less, or 0.1% by mass or more and 2.5% by mass or less, relative to 100% by mass of the monomer.

[0108] The polymerization of the europium complex-containing monomer may be carried out in a solvent. The solvent may be water, or may contain an organic solvent in addition to water. Examples of the organic solvent include one or more selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol, acetone, methyl ethyl ketone, ethyl acetate, isooctane, cyclohexane, benzene, and toluene.

[0109] When radically polymerizing the monomer, a polymerization inhibitor may be added. Examples of the polymerization inhibitor include one or more selected from the group consisting of sodium nitrite, hydroquinone, and potassium hydroquinone sulfonate, with sodium nitrite being preferred.

[0110] When the matrix is ​​inorganic glass, a method for producing europium complex-containing particles can be used, which includes a polymerization step of mixing a silicon precursor with a europium complex and then hydrolyzing and polycondensing the europium complex-containing silicon precursor to obtain europium complex-containing particles. This allows the production of europium complex-containing particles with an inorganic glass matrix. Examples of the silicon precursor include one or more selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate, tetraisobutyl orthosilicate, tetraphenyl orthosilicate, tetravinyl orthosilicate, and tetraallyl orthosilicate.

[0111] When the matrix is ​​an organic low-molecular-weight material, an example of a method for producing europium-complex-containing particles includes a reprecipitation step of mixing the organic low-molecular-weight material and a europium complex in an organic solvent, and then adding a solvent to the europium-complex-containing solution to obtain europium-complex-containing particles. Examples of the organic low molecular weight material include one or more selected from the group consisting of naphthalene, anthracene, phenanthrene, fluoranthene, pyrene, fluorene, and coronene. [Uses of europium complex-containing compositions] The europium complex-containing composition of the present embodiment can be used for known applications, but is preferably used as at least one of a body-worn device and a structural material, and more preferably used as one or more selected from the group consisting of sunscreens and films.

[0112] An example of a body-worn device is a sunscreen comprising a europium complex-containing cell-activating composition. Another example of a body-worn device is a pair of glasses comprising lenses containing a europium complex-containing cell-activating composition. In this case, the lenses are preferably made of a resin containing a europium complex or a glass material laminated with a film of such a resin. Other examples of body-worn devices include sun visors with a brim made of a europium complex-containing cell-activating composition, and fabric products (clothes, hats, masks, etc.) made of a fibrous europium complex-containing cell-activating composition.

[0113] The body-worn device is preferably used as an article that can be attached to an application target. That is, the body-worn device is attached to an application target of red light, and the light is irradiated through the body-worn device. As a result, the red light that passes through the body-worn device is irradiated onto the application target.

[0114] Examples of structural materials include films containing a europium complex-containing cell-activating composition. In this case, the film is preferably composed of a resin containing a europium complex or a glass material laminated with the resin film. The film is installed on walls (including windows) and ceilings in the interior spaces of buildings. It is also installed on walls (including windows) or ceilings in transportation machinery and equipment, specifically front windows, side windows, rear windows, and sunroofs. Other structural materials include window glass containing a europium complex-containing composition for cell activation and netting containing a europium complex-containing composition for cell activation. By irradiating light through the structural material, red light can be applied to the target in the interior space. [Example]

[0115] The present disclosure will be described below with reference to examples, but the present disclosure is not limited thereto.

[0116] The europium complex (1) was identified using the following analytical method. ( 1 H-NMR, 19 F-NMR and 31 P-NMR) 1 H-NMR, 19 F-NMR and 31 P-NMR spectra were measured using ULTRASHIELD PLUS AVANCE III (400 MHz, 376 MHz, and 162 MHz) and ASCEND AVANCE III HD (400 MHz, 376 MHz, and 162 MHz) manufactured by BRUKER. 1 H-NMR was measured using deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6) as a measurement solvent and tetramethylsilane (TMS) as an internal standard. 19 F-NMR and 31 P-NMR was measured using deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6). (UV-Vis absorption spectrum, transmittance spectrum) Measurement was carried out using an ultraviolet-visible-near infrared spectrophotometer (V-670, manufactured by JASCO Corporation) under the following conditions.

[0117] Data acquisition interval: 1 nm Bandwidth 1.0 nm Scanning speed: 400 nm / min Solvent: Chloroform or water (radiation spectrum) An artificial solar lamp (XC-100B, manufactured by Seric Co., Ltd.) was used as the light source, and a portable radiometer (MS-720, manufactured by Eiko Seiki Co., Ltd.) was used as the detector. Measurements were taken under the following conditions.

[0118] Exposure time: 10 seconds Capture wavelength width 1.0 nm (Reference example 1)

[0119] [ka]

[0120] Under an argon atmosphere, pure water (100 mL) was added to europium acetate n-hydrate (8.0 g, 21 mmol as 2.5 hydrate) and stirred at room temperature for 10 minutes to obtain a reaction mixture. Hexafluoroacetylacetone (16.7 g, 80.2 mmol) was added dropwise to the reaction mixture, followed by stirring at 50 °C for 3 hours. The resulting white suspension was filtered, and the resulting white solid was washed with water (200 mL) and toluene (200 mL) to obtain diaquatris(hexafluoroacetylacetonato)europium(III) as a white solid (yield 11.6 g, 68% yield assuming 21 mmol of europium acetate 2.5 hydrate was used). 19 F-NMR(376MHz,Acetone-d6),δ(ppm):-81.2(brs).

[0121] [ka]

[0122] Under an argon atmosphere, ethanol (200 mL) was added to the resulting diaquatris(hexafluoroacetylacetonato)europium(III) (5.0 g, 6.18 mmol) and triphenylphosphine oxide (3.4 g, 12.4 mmol), and the mixture was stirred at 65°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and recrystallized from methanol to give a white solid of Eu(hfa)3(TPPO)2 (bis(triphenylphosphine oxide)tris(hexafluoroacetylacetonato)europium(III)) (yield: 4.8 g, 58%). 19 F-NMR(376MHz, CDCl3), δ(ppm):-79.0(brs). 31 P-NMR(162MHz, CDCl3), δ(ppm):-91.3(brs). (Reference example 2)

[0123] [ka]

[0124] Methanol (5 mL) was added to europium acetate n-hydrate (374 mg, 1.0 mmol as the hemipentahydrate) and tricyclohexylphosphine oxide (593 mg, 2.0 mmol), and the mixture was stirred at room temperature for 1 hour. 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (967 mg, 3.0 mmol) in methanol (2 mL) was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then recrystallized from hexane / methanol. The precipitated powder was washed with methanol to obtain a white solid of bis(tricyclohexylphosphine oxide)tris[4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato]europium(III) (1-10) (yield: 740 mg, 43%). 19 F-NMR(376MHz,CDCl3)δ(ppm):-80.7(brt,J=8.5Hz,9F),-124.5(brq,J=8.5Hz,6F),-127.5(brs,6F). 31P-NMR(162MHz,CDCl3)δ(ppm):-53.6(brs). (Reference example 3)

[0125] [ka]

[0126] To a mixture of 2-naphthol (2.88 g, 20.0 mmol) and cyanoacetic acid (1.70 g, 20.0 mmol), 1,3-dimethyl-2-imidazolidinone (20.0 mL) was added, and trifluoroacetic anhydride (11.3 mL, 80.7 mmol) was added dropwise over 2 h in a room temperature water bath. The mixture was stirred for an additional 22 h. The reaction mixture was poured into water, and the precipitated solid was collected by suction filtration, washed with water, washed with methanol, and dried under vacuum to give 1-hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-one as a yellow solid (yield 2.72 g, 44%). 1 H-NMR(400MHz,CDCl3)δ(ppm):16.50(brs,1H),9.25(brd,J=8.8Hz,1H),8.23(d,J=8.8Hz,1H),7.95(brd, J=8.0Hz,1H),7.80(ddd,J=8.8,7.2,1.6Hz,1H),7.65(ddd,J=8.0,7.2,0.9Hz,1H),7.43(d,J=8.8Hz,1H). 19 F-NMR (376MHz, CDCl3)δ(ppm):-74.2(s,3F).

[0127] [ka]

[0128] Methanol (4.00 mL) was added to europium acetate n-hydrate (75.0 mg, 204 μmol as the hemipentahydrate) and triphenylphosphine oxide (111 mg, 399 μmol) and stirred at room temperature for 1.5 hours. The resulting 1-hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-one (185 mg, 600 μmol) was added to the reaction mixture and stirred at room temperature for 4 hours. The reaction mixture was poured into water, and the precipitated solid was collected by suction filtration and washed with water. This solid was suspended in methylcyclohexane, azeotropically dehydrated, and then allowed to cool. The solid was collected by suction filtration to obtain an ochre solid of tris[1-hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-onato]bis(triphenylphosphine oxide)europium(III) (1-32) (yield: 183 mg, 56% yield from europium acetate 2.5hydrate). 19 F-NMR(376MHz,CDCl3)δ(ppm):-71.4(s,0.5F),-73.4(s,7.3F),-74.0(s,1.2F). 31 P-NMR(162MHz,CDCl3)δ(ppm):-80.7(brs,0.4P),-81.8(brs,1.6P). (Reference example 4)

[0129] [ka]

[0130] 2-Benzofurancarboxylic acid (7.00 g, 43.2 mmol) was dissolved in dichloromethane (86.0 mL). Oxalyl dichloride (6.56 mL, 51.8 mmol) and N,N-dimethylformamide (30 μL, 452 μmol) were added at 0°C, and the mixture was stirred for 4 hours while warming to room temperature. The reaction mixture was concentrated under reduced pressure to obtain crude benzofuran-2-carbonyl chloride (white solid). This crude product was used in the next reaction without further purification. 1H-NMR(400MHz,CDCl3)δ(ppm):7.86(d,J=0.9Hz,1H),7.77(ddd,J=7.9,0.9,0.9Hz,1H),7.64-7.54(m,2H),7.38(ddd,J=8.0,6.9,1.3Hz,1H). 4-Hydroxycoumarin (7.09 g, 43.7 mmol) and benzofuran-2-carbonyl chloride (7.90 g, 47.3 mmol) were dissolved in dichloromethane (150 mL), followed by the addition of N,N-diisopropylethylamine (9.00 mL, 52.9 mmol) and stirring at room temperature for 4 hours. The reaction mixture was washed with 1 M hydrochloric acid (150 mL), saturated aqueous sodium bicarbonate (150 mL), and saturated brine (150 mL). The resulting organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a brown solid. The resulting crude product was dissolved in acetonitrile (150 mL), and acetone cyanohydrin (4.40 mL, 48.1 mmol) and triethylamine (6.70 mL, 48.1 mmol) were added. The mixture was stirred at 50 °C for 48 hours. 1M hydrochloric acid (120.0 mL) was added to the reaction mixture, and the precipitated solid was collected by filtration and washed with water and acetonitrile to give 3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromen-2-one as a yellow solid (yield 4.79 g, 36%). 1 H-NMR(400MHz,CDCl3)δ(ppm):17.11(s,1H),8.38(d,J=1.0Hz,1H),8.13(ddd,J=7.9,1.6,0.4Hz,1H),7.79-7.75(m,1H) ),7.74(ddd,J=8.4,7.3,1.6Hz,1H),7.63(dd,J=8.4,1.0Hz,1H),7.52(ddd,J=8.4,7.3,1.3Hz,1H),7.41-7.31(m,3H).

[0131] [ka]

[0132] Ethanol (15.0 mL) was added to europium(III) acetate hydrate (1.54 g, 4.10 mmol as the hemipentahydrate) and trioctylphosphine oxide (3.17 g, 8.21 mmol) and stirred at room temperature for 1 hour. 3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromen-2-one (3.78 g, 12.3 mmol) was added to the reaction mixture. 14.8 M aqueous ammonia (0.83 mL, 12.2 mmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with 60% aqueous ethanol to give tris[3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III) (1-61) as a yellow oil (yield 7.17 g, 95%). ESIMS (m / z), MeOH: 1863.9 [M+Na]+, 1535.8 [M-(3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromene-2-onato)]+. (Comparative Example 1) 20% by mass of Eu(hfa)3(TPPO)2 obtained in Reference Example 1 and 80% by mass of acrylic resin (G1000, manufactured by Kuraray Co., Ltd.) were kneaded under the following conditions using a Laboplastomill 4C150 (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[0133] Temperature: 180℃ Rotation speed: 60 rpm Mixing time: 10 minutes Thereafter, a europium complex-containing film was produced using a press (manufactured by Kansai Roll Co., Ltd.) under the following conditions so as to have a thickness of 0.1 mm.

[0134] Temperature: 180℃ Rotation speed: 60 rpm Time: 120 seconds Example 1 The europium complex-containing film of this example was produced under the same conditions as in Comparative Example 1, except that 20 mass% of bis(tricyclohexylphosphine oxide)tris[4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato]europium(III) (1-10) obtained in Reference Example 2 was mixed with 80 mass% of acrylic resin (G1000, manufactured by Kuraray Co., Ltd.). Example 2 A europium complex-containing film was produced under the same conditions as in Comparative Example 1, except that 20 mass% of tris[1-hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-onato]bis(triphenylphosphine oxide)europium(III) (1-32) obtained in Reference Example 3 was mixed with 80 mass% of acrylic resin (G1000 manufactured by Kuraray Co., Ltd.). Example 3 An acrylic film containing 20% ​​by mass of tris[3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromene-2-onato]bis(trioctylphosphine oxide)europium(III) (1-61) was used. 25.0 mg of tris[3-(benzofuran-2-carbonyl)-4-hydroxy-2H-chromene-2-onato]bis(trioctylphosphine oxide)europium(III) (1-61) and 100 mg of acrylic resin (Kuraray Co., Ltd., G-1000) were dissolved in 0.5 mL of chloroform, and the resulting acrylic solution was bar-coated onto a white glass plate and air-dried to produce a europium complex-containing film. (Evaluation example 1) The molar absorption coefficients of Eu(hfa)3(TPPO)2, (1-10), (1-32), and (1-61), which are wavelength converting materials prepared in Reference Examples 1 to 4, and phycocyanin (Tokyo Chemical Industry Co., Ltd.) at 350 nm and in the visible light region (blue: 450 nm, green: 550 nm, red: 650 nm) are shown in Table 1. The measurement solvent used for Eu(hfa)3(TPPO)2, (1-10), and (1-32) was chloroform. The measurement solvent used for phycocyanin was water.

[0135] [Table 1]

[0136] Eu(hfa)3(TPPO)2 has a molar absorption coefficient of less than 10,000 at 350 nm, and has poor light absorption ability.

[0137] Phycocyanin absorbs in the visible light range (molar extinction coefficient >10,000), and the solution turns blue. On the other hand, Eu(hfa)3(TPPO)2, (1-10), (1-32), and (1-61) have no or very little absorption in the visible light range (molar extinction coefficient <1,000), and the solution appears colorless and transparent. (Evaluation example 2) A measuring device (MS-720, manufactured by Eiko Seiki Co., Ltd.) was placed 8 cm from the irradiation point of an artificial solar lighting lamp (XC-100B, manufactured by Ceric Co., Ltd.). The europium complex-containing films prepared in Comparative Example 1, Examples 1, and 2 were placed above the detector, and the spectral irradiance was measured. The increase in irradiance of red light (600-630 nm) was evaluated by taking the difference from when the film was not placed. The evaluation results are shown in Table 2. The film using Eu(hfa)3(TPPO)2 (Comparative Example 1) did not increase the irradiance of red light due to its small molar extinction coefficient at 350 nm and poor light absorption ability. Therefore, it was found that it did not have a beneficial effect on skin cells.

[0138] [Table 2]

[0139] (Evaluation example 3) The cell viability measurement test was carried out according to the following procedure. <Pre-culture of human epidermal keratinocytes (NHEK)> Human epidermal keratinocytes (NHEK, Kurabo) were cultured in flasks in medium in a CO2 incubator (5% CO2, 37°C, humidified). Cells were harvested when they reached approximately 80% confluence and used for subsequent experiments. Cells were passaged under the following conditions: After washing with phosphate-buffered saline (PBS, calcium / magnesium-free, glucose / pyruvate-free), they were detached using 0.05% Trypsin-EDTA (Gibco) and neutralized with trypsin neutralizing solution (Kurabo). The cell suspension was then collected in a 15 mL centrifuge tube and centrifuged (room temperature, relative centrifugal force: 180 × g, 5 minutes). The supernatant was removed, and the cells were suspended in fresh medium and counted. The cells were then suspended in medium and seeded at 30,000 cells / well / 100 μL into a 96-well white plate. <Pre-culture of human dermal fibroblasts (HDFa)> Human dermal fibroblasts (HDFa, Thermo Fisher Scientific) were cultured in a flask in growth medium in a CO2 incubator (5% CO2, 37°C, humidified). Cells were harvested when they reached approximately 80% confluence and used for subsequent experiments. Cells were passaged under the following conditions: After washing with PBS (- / -), they were detached using 0.25% Trypsin-EDTA (Nacalai Tesque) and growth medium was added to neutralize the trypsin. The cell suspension was then collected in a 15 mL centrifuge tube and centrifuged (room temperature, relative centrifugal force: 180 × g, 5 minutes). The supernatant was removed, and fresh medium was added to suspend the cells. The cell number was then counted. The cells were suspended in medium and seeded at 10,000 cells / well / 100 μL into a 96-well white plate. <Artificial sunlight irradiation> The day after sowing, the plants were irradiated with artificial sunlight. The irradiance was measured using a measuring instrument (Eiko Seiki MS-720) at a position 8 cm from the irradiating part of an artificial solar lighting lamp (Seric XC-100B), and was found to be approximately 660 W / m 2The artificial sunlight irradiation was carried out in the following manner. The cells were washed three times with phosphate buffered saline (PBS, calcium / magnesium-free, glucose / pyruvic acid-free). After washing, the solution was replaced with Hank's balanced salt solution (HBSS, calcium / magnesium-containing, phenol red-free), and the cells were exposed to artificial sunlight (250 kJ / m²) for 6 minutes without a film, through a UV-cut film (manufactured by Nitto Jushi Kogyo, CLAREX precision plate UV-cut, thickness 0.5 mm), or through the film prepared in Example 2. 2 ), and 12 minutes (500kJ / m 2 During irradiation, the white plate was cooled at 4°C. After irradiation, the medium was replaced with NHEK medium and test medium (HDFa), and the cells were cultured for 24 hours. <Cell viability measurement> After 24 hours of exposure to artificial sunlight, 50 μL of the solution was added to the medium (NHEK) and medium (HDFa) containing the 30% viable cell count reagent SF (Nacalai Tesque) and the absorbance change was measured (final concentration: 10%). 30 and 90 minutes after addition, one-third of the solution was collected and the absorbance was measured (450 nm, reference wavelength: 630 nm). The cell viability was calculated from the change in absorbance per 60 minutes. Cell viability = {(absorbance of test sample - absorbance of blank) ÷ (absorbance of control sample - absorbance of blank)} Test sample: no film, UV-cut film (CLAREX UV Cut, manufactured by Nitto Jushi Kogyo Co., Ltd.), or film prepared in Example 2. Artificial sunlight (250 kJ / m) was irradiated through the film for 6 minutes. 2 ), and 12 minutes (500kJ / m 2 ) Irradiated medium Control sample: medium not exposed to artificial sunlight <Evaluation results> (Human epidermal keratinocytes: NHEK) Table 3 shows the cell viability measured by a cell proliferation assay kit (Wst-8 method, Dojindo Laboratories). Without the film, the viability was less than 20%, and most of the cells were dead. On the other hand, with the UV-cut film, the cell viability was 60-70%. These results demonstrate that UV has a significant effect on the cell viability of human epidermal keratinocytes. Furthermore, by passing the film prepared in Example 2 through the film, the amount of light in the red wavelength region was increased, further reducing damage to the cells.

[0140] [Table 3]

[0141] (Human dermal fibroblasts: HDFa) Table 4 shows the cell viability measured using a cell proliferation assay kit (Wst-8 method, Dojindo Laboratories). Without the film, the viability was less than 30%, and most of the cells were dead. On the other hand, no decrease in cell viability was observed with the UV-blocking film. These results suggest that UV has a significant effect on the cell viability of HDFa. Furthermore, an increase in cell viability was observed when the film prepared in Example 2 was used. Red light enhanced the metabolic activity of the cells or caused cell proliferation.

[0142] [Table 4]

[0143] (Evaluation example 4) The hyaluronic acid production measurement test was carried out according to the following procedure. <Pre-culture of human epidermal keratinocytes (NHEK)> Human epidermal keratinocytes (NHEK, Kurabo) were cultured in flasks in medium in a CO2 incubator (5% CO2, 37°C, humidified). Cells were harvested when they reached approximately 80% confluence and used for subsequent experiments. Cells were passaged under the following conditions: After washing with phosphate-buffered saline (PBS, calcium / magnesium-free, glucose / pyruvate-free), they were detached using 0.05% Trypsin-EDTA (Gibco) and neutralized with trypsin neutralizing solution (Kurabo). The cell suspension was then collected in a 15 mL centrifuge tube and centrifuged (room temperature, relative centrifugal force: 180 × g, 5 minutes). The supernatant was removed, and the cells were suspended in fresh medium and counted. The cells were then suspended in medium and seeded into a 96-well white plate at 10,000 cells / well / 100 μL. <Artificial sunlight irradiation> The day after sowing, the plants were irradiated with artificial sunlight. The irradiance was measured using a measuring instrument (Eiko Seiki MS-720) at a position 8 cm from the irradiating part of an artificial solar lighting lamp (Seric XC-100B), and was found to be approximately 660 W / m 2 The artificial sunlight irradiation was carried out in the following manner. The cells were washed three times with phosphate buffered saline (PBS, calcium / magnesium-free, glucose / pyruvic acid-free). After washing, the solution was replaced with Hank's balanced salt solution (HBSS, calcium / magnesium-containing, phenol red-free), and the cells were exposed to artificial sunlight (250 kJ / m²) for 6 minutes through a UV-cut film (manufactured by Nitto Jushi Kogyo Co., Ltd., CLAREX precision plate, UV-cut, thickness 0.5 mm) or the film prepared in Example 2. 2 During irradiation, the white plate was cooled at 4°C. After irradiation, the medium was replaced with test medium (HDFa) and cultured for 24 hours. <Evaluation results> (Evaluation of hyaluronic acid production) Hyaluronic acid production was evaluated using a hyaluronic acid measurement kit (K-1200, Echelon Biosciences). A sample of cells not exposed to artificial sunlight was used as a control sample, and the results are shown in Table 5. The control sample (not exposed to artificial sunlight) had a hyaluronic acid production of 305 ng / mL. On the other hand, with the UV-cut film, a decrease in hyaluronic acid production was observed, with a production of 250 ng / mL. These results suggest that the hyaluronic acid production of NHEK is reduced by the influence of artificial sunlight. Furthermore, the hyaluronic acid production increased to 348 ng / mL when the film prepared in Example 2 was used. It was found that red light promoted hyaluronic acid production of NHEK.

[0144] [Table 5] [Explanation of symbols]

[0145] 100,200 Europium complex-containing cell stimulating composition 10,20 Europium complexes 11,21 Medium 22 Matrix consisting of one or more selected from the group consisting of resin materials, inorganic glass, and organic low molecular weight materials

Claims

1. One or more materials selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low-molecular-weight materials, and a molar absorption coefficient at a wavelength of 350 nm of 10,000 L mol －１ ・cm －１ A europium complex-containing cell stimulating composition comprising the above europium complex.

2. 2. The europium complex-containing cell-stimulating composition according to claim 1, wherein the europium complex is a europium complex represented by general formula (1): 【Chemical 1】 {HC is a ligand represented by general formula (1dk), general formula (1qu), or general formula (1cu). 【Chemistry 2】 [In the formula, each V independently represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a hydrogen atom, an aryl group having 6 to 22 carbon atoms, or a thienyl group.] 【Chemistry 3】 [In the formula, R Ａ represents a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 22 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R Ｂ１ , R Ｂ２ , R Ｂ３ , R Ｂ４ and R Ｂ５ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Also, R Ｂ１ , R Ｂ２ , R Ｂ３ and R Ｂ４ Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring. 【Chemistry 4】 [In the formula, R Ａ is R in general formula (1qu). Ａ It has the same meaning as: R Ｃ１ , R Ｃ２ , R Ｃ３ and R Ｃ４ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. In addition, the substituent R Ｃ１ , R Ｃ２ , R Ｃ３ and R Ｃ４ Two adjacent substituents may be bonded to the benzene ring to form a 5-, 6-, or 7-membered ring. n represents 1, 2 or 3. When n is 2 or 3, the ligands may be the same or different. L represents a nitrogen-containing ligand having two or more nitrogen atoms having an unshared electron pair or a phosphine oxide ligand. m represents 0, 1 or 2; When m is 2, L may be the same or different.

3. 3. The europium complex-containing cell-stimulating composition according to claim 1, wherein n is 3.

4. 2. The europium complex-containing cell-stimulating composition according to claim 1, wherein the europium complex is a europium complex represented by any one of the following formulas (1-1) to (1-63): 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】

5. 3. The europium complex-containing cell-stimulating composition according to claim 1, comprising europium complex-containing particles containing one or more materials selected from the group consisting of resin materials, inorganic glass, and organic low molecular weight materials, and the europium complex; and one or more materials selected from the group consisting of resin materials, inorganic glass, liquid materials, and organic low molecular weight materials.

6. A body-worn device comprising the europium complex-containing cell stimulating composition according to claim 1 or 2.

7. A structural material comprising the europium complex-containing cell stimulating composition according to claim 1 or 2.

Images