Rare earth complex-containing polymer composition and method for producing the same

Abstract

To provide at least one of a polymer composition and a method for producing the same, the polymer composition being excellent in both the light resistance and the wavelength conversion function with respect to near-ultraviolet light.SOLUTION: A rare earth complex-containing polymer composition comprises: a rare earth complex represented by general formula (1); and one or more polymers selected from the group consisting of polymethyl methacrylate, polybutyl methacrylate, fluorine-containing acrylic resin, and polystyrene, where the average particle diameter is 5 μm or more and 150 μm or less. [Ln represents a trivalent rare earth ion.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a rare earth complex-containing polymer composition and a method for producing the same.

Background Art

[0002] In protected cultivation for growing plants in a greenhouse for agriculture, measures have been taken to significantly improve both the yield and quality of crops compared to open-field cultivation. For example, for the purpose of further improving the yield and quality of crops, adjusting the harvest time, shortening the cultivation period, etc., studies have been conducted to impart to the film used in the greenhouse for agriculture a function of converting ultraviolet light with low photosynthesis efficiency and green to yellow light into blue light or orange to red light with high photosynthesis efficiency.

[0003] As a means of imparting the above function to an agricultural film, Patent Document 1 discloses an agricultural film in which a polymer composition containing a material (hereinafter also referred to as a "wavelength conversion material") having a function of converting light of a specific wavelength into light of a different wavelength (hereinafter also referred to as a "wavelength conversion function") is laminated.

[0004] In recent years, as an excellent wavelength conversion material, Patent Document 2 has disclosed a rare earth complex having a β-diketonato ligand and a phosphine oxide ligand.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the practical application of an agricultural film containing a wavelength conversion material, it is necessary to have both high light resistance and a high wavelength conversion function for near-ultraviolet light. However, the coexistence of high light resistance and a high wavelength conversion function for near-ultraviolet light has not been achieved, and its application to agricultural films is difficult.

[0007] An object of the present disclosure is to provide at least one of a rare earth complex-containing polymer composition excellent in both light resistance and a wavelength conversion function for near-ultraviolet light and a method for producing the same.

Means for Solving the Problems

[0008] The inventors of the present invention have found that by using a rare earth complex having a specific structure to obtain a rare earth complex-containing polymer having a specific average particle size, a polymer composition excellent in both light resistance and a wavelength conversion function for near-ultraviolet light can be obtained.

[0009] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows. [1] A rare earth complex-containing polymer composition containing a rare earth complex represented by the general formula (1) and one or more polymers selected from the group consisting of polymethyl methacrylate, polybutyl methacrylate, a fluorine-containing acrylic resin, and polystyrene, and having an average particle size of 5 μm or more and 150 μm or less.

[0010]

Chemical formula

[0011] [In the formula, R 1 represents a haloalkyl group having 1 to 6 carbon atoms. R 2 , R 3 , R 4 and R 5Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms which may be substituted with an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms which may be substituted with a halogen atom. Also, R 2 , R 3 , R 4 and R 5 Among them, two adjacent substituents may combine with the benzene ring to which they are attached to form a 5-membered, 6-membered or 7-membered ring. [In the formula, X 1 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group represented by the following general formula (2).

[0012] [Chemical formula]

[0013] (In the formula, X 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 4 to 12 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms or a haloalkyloxy group having 1 to 6 carbon atoms, and the aryl group may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkyloxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group and a nitro group.) Ln represents a trivalent rare earth ion. [2] The rare earth complex-containing polymer composition according to [1] above, wherein Ln is europium ion (III). [3] R 2 , R 3 , R 4 and R 5The rare earth complex-containing polymer composition according to the above [1] or [2], wherein all are hydrogen atoms. [4] A polymerization step of mixing a monomer and a rare earth complex (1) and polymerizing the rare earth complex-containing monomer to obtain rare earth complex-containing polymer fine particles, the method for producing a rare earth complex-containing polymer composition according to any one of the above [1] to [3].

Effect of the Invention

[0014] According to the present disclosure, at least one of a polymer composition excellent in both light resistance and wavelength conversion function for near ultraviolet rays and a method for producing the same can be provided.

Brief Description of the Drawings

[0015]

Figure 1

Modes for Carrying Out the Invention

[0016] Hereinafter, the present disclosure will be described in detail. However, the embodiments described below are examples of the present disclosure, and the present disclosure is not limited to these contents. In addition, each configuration and parameter disclosed in this specification can be arbitrarily combined, and any combination of the upper and lower limits of the values disclosed in this specification is also included in the present disclosure. [Rare Earth Complex-Containing Polymer Composition] This embodiment is A rare earth complex-containing polymer composition containing a rare earth complex represented by the general formula (1) and one or more polymers selected from the group consisting of polymethyl methacrylate, polybutyl methacrylate, fluorine-containing acrylic resin, and polystyrene, and having an average particle diameter of 5 μm or more and 150 μm or less.

[0017] [Chemical formula]

[0018] [In the formula, R 1 represents a haloalkyl group having 1 to 6 carbon atoms. R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms which may be substituted with an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms which may be substituted with a halogen atom. Also, among R 2 , R 3 , R 4 and R 5 , two adjacent substituents may combine with the benzene ring to form a 5-membered, 6-membered or 7-membered ring.] [In the formula, X 1 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group represented by the following general formula (2). X 1 may be the same or different from each other.

[0019] [Chemical formula]

[0020] (In the formula, X 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 4 to 12 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, or a haloalkyloxy group having 1 to 6 carbon atoms. X 2 may be the same or different from each other.) Ln represents a trivalent rare earth ion. The rare earth complex-containing polymer composition of this embodiment can be used as a wavelength conversion material.

[0021] The rare earth complex-containing polymer composition of this embodiment contains one or more polymers selected from the group consisting of polymethyl methacrylate, polybutyl methacrylate, fluorine-containing acrylic resin, and polystyrene. In terms of high gas barrier properties, it is preferable that the rare earth complex-containing polymer composition of this embodiment contains at least one of methyl methacrylate and butyl methacrylate polymers, and it is more preferable to contain methyl methacrylate in terms of low raw material cost.

[0022] The rare earth complex-containing polymer composition of this embodiment preferably contains divinylbenzene. By containing divinylbenzene, the polymer contained in the rare earth complex-containing polymer composition of this embodiment is crosslinked, and the light resistance is likely to be improved. The content of divinylbenzene can be exemplified as 0.01% by mass or more, 0.1% by mass or more, or 0.4% by mass or more. When the content of divinylbenzene increases, the crosslinking of the polymer tends to proceed. The upper limit of the content of divinylbenzene can be exemplified as 99% by mass or less, 90% by mass or less, or 75% by mass or less.

[0023] The form of the rare earth complex-containing polymer composition of this embodiment is arbitrary, and examples include being in powder form, and further being a composition composed of particles.

[0024] The average particle diameter of the rare earth complex-containing polymer composition of this embodiment is 5 μm or more and 150 μm or less. If the average particle diameter is larger than 150 μm, defects are likely to occur in the agricultural film to which the rare earth complex-containing polymer composition is added. If the average particle diameter is smaller than 5 μm, the polymer particles are likely to scatter and the particles are likely to aggregate with each other. The average particle diameter of the rare earth complex-containing polymer is 5 μm or more, and it can be exemplified as 6 μm or more or 7 μm or more. Further, the upper limit of the average particle diameter of the rare earth complex-containing polymer is 150 μm or less, and it can be exemplified as 30 μm or less or 10 μm or less. The average particle diameter of the rare earth complex-containing polymer is preferably 5 μm or more and 30 μm or less, and more preferably 6 μm or more and 10 μm or less. The average particle diameter of the rare earth complex-containing polymer composition of this embodiment can be obtained by dispersing this in pure water, using a general particle diameter distribution measuring device (manufactured by Microtrac Bell Co., Ltd., Microtrac MT3300EXII), measuring the volume particle size distribution by the laser diffraction scattering method under the following conditions, and taking the obtained median diameter as the average particle diameter.

[0025] Shape of particles: Non-spherical Number of measurements: 3 times Measurement time: 30 seconds Refractive index: 1.49 The content of the polymer in the rare earth complex-containing polymer composition of this embodiment can be exemplified as 1 mass% or more, 25 mass% or more, or 50 mass% or more, and can be exemplified as 99.99 mass% or less, 99.9 mass% or less, or 99 mass% or less. The content of the polymer is preferably 1 mass% or more and 99.99 mass% or less, and more preferably 25 mass% or more and 99.9 mass%.

[0026] The content of the polymer in the rare earth complex-containing polymer composition of this embodiment is the entire remaining amount obtained by subtracting the content of the rare earth complex from the weight of the rare earth complex-containing polymer composition.

[0027] The rare earth complex-containing polymer composition of this embodiment contains a rare earth complex represented by the general formula (1) (hereinafter, also referred to as "rare earth complex (1)"). The rare earth complex (1) contained in the rare earth complex-containing polymer composition of this embodiment exists in a state where the rare earth complex (1) is dispersed in the particles constituting the rare earth complex-containing polymer composition. As the content of the rare earth complex (1), it can be exemplified as 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and it can be exemplified as 99% by mass or less, 75% by mass or less, or 50% by mass or less. The content of the rare earth complex (1) is preferably 0.01% by mass or more and 99% by mass or less, and more preferably 0.05% by mass or more and 75% by mass or less.

[0028] The content of the rare earth complex in the rare earth complex-containing polymer composition of this embodiment may be determined by ICP-AES measurement. The ICP-AES measurement determines the content obtained by converting the content of the rare earth element measured using a general ICP-AES apparatus (for example, 5800 ICP-OES manufactured by Agilent Technologies) into a rare earth complex. The content of the rare earth complex may be the mass ratio (% by mass) of the obtained converted content to the weight of the rare earth complex-containing polymer composition.

[0029] The rare earth complex-containing polymer composition of this embodiment preferably has a composition that is 100% by mass of the polymer and the rare earth complex (1), but may contain components other than the polymer and the rare earth complex (1) as long as the effects are achieved. Examples of other components include unreacted monomers during polymer synthesis, organic solvents during the synthesis of the rare earth complex (1), and one or more selected from the group of ligands of the rare earth complex (1). [Rare earth complex (1)] Next, each substituent in the rare earth complex (1) contained in the rare earth complex-containing polymer composition of this embodiment will be described respectively. In this specification, a hydrogen atom includes a deuterium atom and a tritium atom.

[0030] [Chemical formula]

[0031] (wherein R 1 , R 2 , R 3 , R 4 , R 5 and X 1 represent the same meanings as R 1 , R 2 , R 3 , R 4 , R 5 and X 1 in the general formula (1). Ln represents a trivalent rare earth ion.) (Regarding Ln) The above-mentioned Ln is a trivalent rare earth ion, specifically, scandium ion (III), yttrium ion (III), lanthanum ion (III), cerium ion (III), praseodymium ion (III), neodymium ion (III), promethium ion (III), samarium ion (III), europium ion (III), gadolinium ion (III), terbium ion (III), dysprosium ion (III), holmium ion (III), erbium ion (III), thulium ion (III), ytterbium ion (III), and lutetium ion (III). Among them, europium ion (III) or terbium ion (III) is preferable in that it has an emission wavelength in the visible light region used for plant photosynthesis, and europium ion (III) is more preferable in that it emits red light with high utilization efficiency for photosynthesis.)

[0032] Next, R 1 , R 2 , R 3 , R 4 and R 5 will be described respectively.)

[0033] (Regarding R 1 ) R 1Examples of the C1-C6 haloalkyl group represented by include linear or branched haloalkyl groups. Specifically, they include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoropropan-2-yl group, 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-nonafluorobutan-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-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 of such groups 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, 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, and 3-bromopropyl group. A trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a perfluoropropyl group is preferred because the raw materials are readily available, and a trifluoromethyl group is more preferred because the raw materials are inexpensive.

[0034] R 1 Examples of the halocycloalkyl group having 3 to 6 carbon atoms represented by the following formula include a perfluorocyclopentyl group, a perfluorocyclohexyl group, and a perfluorocyclopentylmethyl group.

[0035] (R 2 , R 3 , R 4 and R 5 About R 2 , R 3 , R 4 and R 5 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0036] R 2 , R 3 , R 4 and R 5The 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.

[0037] R 2 , R 3 , R 4 and R 5 Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by the formula (1) 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.

[0038] R 2 , R 3 , R 4 and R 5The alkenyl group having 2 to 4 carbon atoms which may be substituted with an alkyloxy group having 1 to 6 carbon atoms, represented by the formula (I), may be either a linear or branched alkenyl group, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 2-methylallyl group, a 1-methoxyvinyl group, a 2-methoxyvinyl group, a 1-ethoxyvinyl group, a 2-ethoxyvinyl group, a 1-isopropyloxyvinyl group, a 2-isopropyloxyvinyl group, a 1-(tert-butyl)oxyvinyl group, a 2-(tert-butyl)oxyvinyl group, a 1-hexyloxyvinyl group, and a 2-hexyloxyvinyl group.

[0039] R 2 , R 3 , R 4 and R 5 The haloalkyl group having 1 to 6 carbon atoms represented by the formula: 1 Examples of the substituent include those exemplified as the haloalkyl group having 1 to 6 carbon atoms represented by the following formula:

[0040] R 2 , R 3 , R 4 and R 5 The halocycloalkyl group having 3 to 6 carbon atoms represented by the formula: 1 Examples of the substituent include those exemplified as the haloalkyl group having 3 to 6 carbon atoms represented by the following formula:

[0041] R 2 , R 3 , R 4 and R 5Examples of the aryl group having 6 to 14 carbon atoms represented by include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl 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, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl)phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 9-anthryl group, 2-phenanthrenyl group, 3-phenanthrenyl group, and 9-phenanthrenyl group.

[0042] R 2 , R 3 , R 4 and R 5Specific examples of the aralkyl group having 7 to 14 carbon atoms and optionally substituted with a halogen atom, represented by the formula (I) above, include a benzyl group, a phenethyl group, a (4-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (2-methylphenyl)methyl group, a (4-fluorophenyl)methyl group, a (3-fluorophenyl)methyl group, a (2-fluorophenyl)methyl group, a (4-bromophenyl)methyl group, a (4-chlorophenyl)methyl group, a (4-iodophenyl)methyl group, a (4-trifluoromethylphenyl)methyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, a (6-fluoronaphthalene-2-yl)methyl group, a (4-fluoronaphthalene-1-yl)methyl group, and a (6-trifluoromethylnaphthalene-2-yl)methyl group.

[0043] R 2 , R 3 , R 4 and R 5 Among these, two adjacent substituents (e.g., R 2 and R 3 ) may form a 5-, 6-, or 7-membered ring together with the benzene ring to which it is bonded, and specific examples thereof include a butadiene-1,4-diyl group, a methylenedioxy group, and an ethylenedioxy group.

[0044] R 2 , R 3 , R 4 and R 5 At least one of the groups is preferably a hydrogen atom or a butadiene-1,4-diyl group, in that it has a high wavelength conversion function for near ultraviolet light, and it is more preferable that both are hydrogen atoms, in that the raw materials are easily available.

[0045] (X 1 About X in general formula (1) 1 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group represented by general formula (2). 1 may be the same or different.

[0046] X 1 Examples of the alkyl group having 1 to 10 carbon atoms represented by R 2 、R 3 、R 4 and R 5 include the groups exemplified as the alkyl group having 1 to 10 carbon atoms. From the viewpoint of easy availability of raw materials, an octyl group, a butyl group, or a tert-butyl group is preferable, and an octyl group is more preferable in terms of having suitable optical properties as an optical functional material.

[0047] X 1 Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R 2 、R 3 、R 4 and R 5 include the groups exemplified as the cycloalkyl group having 3 to 10 carbon atoms. From the viewpoint of easy availability of raw materials, a cyclohexyl group is preferable (Regarding X 2 ) X in the general formula (2) 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 4 to 12 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, or a haloalkyloxy group having 1 to 6 carbon atoms. X 2 may be the same or different from each other.

[0048] X 2 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0049] X 2Examples of the alkyl group having 1 to 6 carbon atoms represented by 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 3-cyclopropylpropyl 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, a 1-ethylpropyl group, and a hexyl group.

[0050] X 2 Examples of the cycloalkyl group having 3 to 6 carbon atoms represented by include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0051] X 2 Examples of the alkyloxy group having 1 to 6 carbon atoms represented by may be linear, branched or cyclic, and specifically include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a 2-methylpropyloxy group, a 2,2-dimethylpropyloxy group, a 3-cyclopropylpropyloxy group, a cyclopropyloxy group, a 2-methylbutyloxy group, a 3-methylbutyloxy group, a tert-butyloxy group, a cyclobutyloxy group, a pentyloxy group, a 2-methylpentyloxy group, a 1-methylbutyloxy group, a 1,2-dimethylbutyloxy group, a 1-ethylpropyloxy group, a cyclopentyloxy group, a hexyloxy group, and a cyclohexyloxy group.

[0052] X 2Examples of the aryl group having 6 to 14 carbon atoms represented by include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl 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, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl)phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 9-anthryl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 9-phenanthrenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 2-(perfluoropropyl)phenyl group,3-(Perfluoropropyl)phenyl group, 4-(perfluoropropyl)phenyl group, 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 2-pivaloyl phenyl group, 3-pivaloyl phenyl group, 4-pivaloyl phenyl group, 2-benzoyl phenyl group, 3-benzoyl phenyl group, 4-benzoyl phenyl group, 2-naphthoyl phenyl group, 3-naphthoyl phenyl group, 4-naphthoyl phenyl group, 4-methoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 4'-methoxybiphenyl-2-yl group, 4'-methoxybiphenyl-3-yl group, 4'-methoxybiphenyl-4-yl group, 10-methoxy-9-anthryl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,4-difluorophenyl group, 4-(trifluoromethyloxy)phenyl group, 4-phenyloxyphenyl group, 4-(phenylamino)phenyl group, 4-(diphenylamino)phenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-hydroxyphenyl group, and deuterated phenyl group can be exemplified. In terms of having optical properties suitable for optical functional materials, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,4-difluorophenyl group, 2-(diphenylamino)phenyl group, 3-(diphenylamino)phenyl group, 4-(diphenylamino)phenyl group, deuterated phenyl group, perfluorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-{bis[4-(trifluoromethyl)phenyl]amino}phenyl group, 4-{bis[4-bis(4-cyanophenyl)amino]phenyl group, 4-{bis[4-bis(3,5-difluorophenyl)amino]phenyl group, or 4-[bis(4-fluorophenyl)amino]phenyl group is preferred, and phenyl group, 4-(trifluoromethyl)phenyl group is preferred in terms of ease of synthesis.Or a 4-(diphenylamino)phenyl group is more preferred.,

[0053] X 2Examples of the heteroaryl group having 4 to 12 carbon atoms represented by include 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-methylpyrrol-2-yl, 1-methylpyrrol-3-yl, 1-phenylpyrrol-2-yl, 1-phenylpyrrol-3-yl, 2-benzofuranyl, 3-benzofuranyl, 2-benzothienyl, 3-benzothienyl, 1-indolyl, 2-indolyl, 3-indolyl, 1-methylindol-2-yl, 1-methylindol-3-yl, 1-phenylindol-2-yl, 1-phenylindol-3-yl, 9-methylcarbazol-2-yl, 9-methylcarbazol-3-yl, 9-ethylcarbazol-2-yl, 9-ethylcarbazol-3-yl, 9-phenylcarbazol-2-yl, 9-phenylcarbazol-3-yl, dibenzofuran-2-yl, dibenzofuran-3-yl, dibenzofuran-4-yl, dibenzothiophene-2-yl, dibenzothiophene-3-yl, dibenzothiophene-4-yl, 5-(trifluoromethyl)fur-2-yl, 2-(trifluoromethyl)fur-3-yl, 5-(trifluoromethyl)thiophen-2-yl, 2-(trifluoromethyl)-3-thienyl, 5-(trifluoromethyl)benzofuran-2-yl, 6-(trifluoromethyl)benzofuran-2-yl, 5-(trifluoromethyl)benzothiophene-2-yl, 6-(trifluoromethyl)benzothiophene-2-yl, 9-methyl-5-(trifluoromethyl)carbazol-2-yl, 9-methyl-6-(trifluoromethyl)carbazol-2-yl, 9-methyl-5-(trifluoromethyl)carbazol-3-yl, 9-methyl-6-(trifluoromethyl)carbazol-3-yl, 9-phenyl-5-(trifluoromethyl)carbazol-2-yl, 9-phenyl-5-(trifluoromethyl)carbazol-3-yl, 9-phenyl-6-(trifluoromethyl)carbazol-2-yl, 9-phenyl-6-(trifluoromethyl)carbazol-3-yl, 6-(trifluoromethyl)dibenzofuran-2-yl,7-(Trifluoromethyl)dibenzofuran-2-yl group, 6-(trifluoromethyl)dibenzofuran-3-yl group, 7-(trifluoromethyl)dibenzofuran-3-yl group, 6-(trifluoromethyl)dibenzofuran-4-yl group, 7-(trifluoromethyl)dibenzofuran-4-yl group, 6-(trifluoromethyl)dibenzothiophen-2-yl group, 7-(trifluoromethyl)dibenzothiophen-2-yl group, 6-(trifluoromethyl)dibenzothiophen-3-yl group, 7-(trifluoromethyl)dibenzothiophen-3-yl group, 6-(trifluoromethyl)dibenzothiophen-4-yl group, and 7-(trifluoromethyl)dibenzothiophen-4-yl group can be exemplified. In terms of easy synthesis, 2-furanyl group, 2-thienyl group, 2-benzofuranyl group, 2-benzothienyl group, 9-methylcarbazol-3-yl group, 9-ethylcarbazol-3-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, 5-(trifluoromethyl)furan-2-yl group, or 5-(trifluoromethyl)thiophen-2-yl group is preferable, and in terms of inexpensive raw materials, 2-furanyl group, 2-thienyl group, 2-benzofuranyl group, or 2-benzothienyl group is more preferable.

[0054] X 2Examples of the aryloxy group having 5 to 14 carbon atoms represented by include an indenyl-oxy group, a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a 2,3-dimethylphenyloxy group, a 2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a 2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a 3,5-dimethylphenyloxy group, a 2,3,4-trimethylphenyloxy group, a 2,3,5-trimethylphenyloxy group, a 2,3,6-trimethylphenyloxy group, a 2,4,5-trimethylphenyloxy group, a 2,4,6-trimethylphenyloxy group, a 3,4,5-trimethylphenyloxy group, a 2,3,4,5-tetramethylphenyloxy group, a 2,3,4,6-tetramethylphenyloxy group, a 2,3,5,6-tetramethylphenyloxy group, a 2-ethylphenyloxy group, a 3-ethylphenyloxy group, a 4-ethylphenyloxy group, a 2,3-diethylphenyloxy group, a 2,4-diethylphenyloxy group, a 2,5-diethylphenyloxy group, a 2,6-diethylphenyloxy group, a 3,4-diethylphenyloxy group, a 3,Examples thereof include a 5 - diethylphenyloxy group, a 2 - propylphenyloxy group, a 3 - propylphenyloxy group, a 4 - propylphenyloxy group, a 2 - isopropylphenyloxy group, a 3 - isopropylphenyloxy group, a 4 - isopropylphenyloxy group, a 2 - cyclopropylphenyloxy group, a 3 - cyclopropylphenyloxy group, a 4 - cyclopropylphenyloxy group, a 2 - butylphenyloxy group, a 3 - butylphenyloxy group, a 4 - butylphenyloxy group, a 2-(1 - methylpropyl)phenyloxy group, a 3-(1 - methylpropyl)phenyloxy group, a 4-(1 - methylpropyl)phenyloxy group, a 2-(2 - methylpropyl)phenyloxy group, a 3-(2 - methylpropyl)phenyloxy group, a 4-(2 - methylpropyl)phenyloxy group, a 2 - cyclobutylphenyloxy group, a 3 - cyclobutylphenyloxy group, a 4 - cyclobutylphenyloxy group, a (biphenyl - 2 - yl)oxy group, a (biphenyl - 3 - yl)oxy group, a (biphenyl - 4 - yl)oxy group, a (phenanthren - 9 - yl)oxy group, and an (anthracen - 9 - yl)oxy group.,

[0055] X 2 Examples of the haloalkyl group having 1 to 6 carbon atoms represented by R 1 include the haloalkyl groups having 1 to 6 carbon atoms exemplified in R

[0056] X 2 Examples of the halocycloalkyl group having 3 to 6 carbon atoms represented by R 1 include the halocycloalkyl groups having 3 to 6 carbon atoms exemplified in R

[0057] X 2Examples of the C1-C6 haloalkyloxy group represented by include linear, branched, or cyclic haloalkyloxy groups. Specifically, they include trifluoromethyloxy group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-fluoroethyloxy group, perfluoropropyloxy group, 2,2,3,3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1,1-difluoropropyloxy group, 1,1,1,2,3,3,3-heptafluoropropan-2-yloxy group, 1,1,1,3,3,3-hexafluoropropan-2-yloxy group, perfluoropentyloxy group, perfluorocyclopentyloxy group, perfluorohexyloxy group, perfluorocyclohexyloxy group, chloromethyloxy group, bromomethyloxy group, iodomethyloxy group, 2-chloroethyloxy group, 3-bromopropyloxy group, and 3-iodopropyloxy group.

[0058] (L 1 with respect to) L 1 represents a phosphorus ligand represented by the following general formula (3).

[0059]

Chemical formula

[0060] L 1 As , in terms of having optical properties suitable for an optical functional material, X in the general formula (3) 1 is an alkyl group having 4 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or an aryl group represented by the general formula (2) in which X 2 is a hydrogen atom, a halogen atom, or a phenyl group. A phosphorus ligand is preferred. In terms of the raw materials being easily available, X in the general formula (3) 1 is an alkyl group having 4 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or X 2It is more preferable that the aryl group represented by the general formula (2) is a hydrogen atom.

[0061] The alkyl group having 4 to 8 carbon atoms may be either a linear or branched alkyl group. Specifically, examples thereof include a butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and octyl group. From the viewpoint of easy availability of raw materials, a butyl group, tert-butyl group, or octyl group is preferable, and from the viewpoint of easy synthesis, a butyl group or octyl group is more preferable.

[0062] Examples of the cycloalkyl group having 4 to 8 carbon atoms include a cyclobutyl group, cyclopentyl group, 5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, cycloheptyl group, and cyclooctyl group. From the viewpoint of easy availability of raw materials, a cyclopentyl group or cyclohexyl group is preferable, and from the viewpoint of easy synthesis, a cyclohexyl group is more preferable.

[0063] The phosphorus ligand L represented by the general formula (3) 1 Examples thereof include triphenylphosphine oxide, cyclohexyldiphenylphosphine oxide, tri(p-tolyl)phosphine oxide, triphenylphosphine oxide-d 15 , tributylphosphine oxide, tri(tert-butyl)phosphine oxide, trioctylphosphine oxide, tricyclohexylphosphine oxide, dicyclohexylphenylphosphine oxide, dicyclohexyl(o-tolyl)phosphine oxide, 2-biphenylyldicyclohexylphosphine oxide, tripentylphosphine oxide, 2-biphenylyldiphenylphosphine oxide, tri(o-tolyl)phosphine oxide, or tris(2-methoxyphenyl)phosphine oxide, with triphenylphosphine oxide or tricyclohexylphosphine oxide being more preferable.

[0064] The polymer composition of this embodiment may contain a crystallization solvent during purification by reprecipitation, recrystallization, or the like.

[0065] Specific examples of the rare earth complex (1) include one or more rare earth complexes represented by the group of the following formulas (1-1) to (1-18).

[0066] [Chemical formula]

[0067] Among the above formulas (1-1) to (1-18), in terms of easy availability of raw materials, the compounds represented by formulas (1-1) to (1-7) are preferable, and in terms of easy synthesis, any one selected from the group of compounds represented by formulas (1-5) to (1-7) is more preferable. [Method for producing rare earth complex] Next, the method for producing the rare earth complex (1) contained in the polymer composition of this embodiment will be described.

[0068] (Production method 1)

[0069] [Chemical formula]

[0070] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , Ln and L 1 represent the same meanings as R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , Ln and L 1 in the general formula (1).).

[0071] As a method for producing the rare earth complex (1), enol represented by the following general formula (4) (hereinafter referred to as enol (4)), and L 1 A production method 1 (hereinafter also referred to as "method 1") characterized by reacting the phosphorus ligand represented by the general formula (3) with a rare earth compound can be mentioned.

[0072] In method 1, R 1 、R 2 、R 3 、R 4 、R 5 、X 1 、Ln and L 1 For the definitions and specific examples shown in, R in the general formula (1) 1 、R 2 、R 3 、R 4 、R 5 、X 1 、Ln and L 1 Are the same as.

[0073] L 1 Can be obtained by the methods described in Chemical Reviews, Vol. 60, pp. 243-260, 1960, etc. Commercially available products may also be used.

[0074] The enol (4) used in method 1 can be obtained, for example, by the methods 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, etc. Commercially available products may also be used.

[0075] The enol (4) used in Method 1 loses its active proton when a base acts on it and becomes an organic salt shown in the above formula (5). This organic salt (5) may be used as the enol (4), and C shown as the counter cation of the organic salt (5) at that time A+ Specific examples of C 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.

[0076] The rare earth compounds used in Method 1 include, for example, as europium compounds, 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(III) acetate hydrate, europium(III) trifluoroacetate hydrate, europium(III) trifluoromethanesulfonate hydrate, tris[N,N-bis(trimethylsilyl)amide]europium(III), europium(III) trimethoxide, europium(III) triethoxide, and europium(III) tri(isopropoxide), 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 yields, 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, and europium(III) trifluoromethanesulfonate hydrate are preferred, and europium(III) acetate, europium(III) chloride, europium(III) nitrate, europium(III) acetate hydrate, europium(III) chloride hydrate, or europium(III) nitrate hydrate are more preferred.

[0077] Commercially available products can be used as the rare earth compounds used in Method 1.

[0078] In Method 1, it is preferable to carry out the reaction in a solvent in terms of the good yield of the rare earth complex (1). The type of the solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent 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 thereof in any ratio. Chloroform, methylcyclohexane, acetone, methanol, ethanol, toluene, or water is preferable in terms of the good reaction yield of the obtained rare earth complex (1).

[0079] The molar ratio of the rare earth compound and enol (4) in Method 1 will be described. It is preferable to use 1.0 to 5.0 moles of enol (4) with respect to 1 mole of the rare earth compound, and more preferably 3.0 to 4.0 moles of enol (4).

[0080] The molar ratio of the rare earth compound and phosphorus ligand (3) in Method 1 will be described. 0.5 to 5.0 moles of L 1 is preferably used with respect to 1 mole of the rare earth compound, and more preferably 1.0 to 3.0 moles of L 1 is used.

[0081] In Method 1, a base may be added to promote the reaction. Examples of the base include trimethylamine, triethylamine, diethylamine, pyridine, quinoline, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide. As the equivalent of the base, it is preferable to use 1.0 mol or more and 10 mol or less of the base per 1 mol of enol (4), more preferably 2.0 mol or more and 8.0 mol or less of the base, and still more preferably 3.0 mol or more and 5.0 mol or less of the base.

[0082] In Method 1, there are no particular restrictions on the reaction temperature and reaction time, and general conditions used by those skilled in the art when manufacturing metal complexes can be employed. As a specific example, the rare earth complex (1) can be produced in good yield by appropriately selecting a reaction time of 1 minute or more and 120 hours or less at a reaction temperature of -80°C or higher and 120°C or lower.

[0083] The rare earth complex (1) produced by Method 1 can be purified by appropriately selecting a general purification method used by those skilled in the art when purifying metal complexes. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, precipitation, and column chromatography.

[0084] (Production Method 2) As another production method of the rare earth complex (1) contained in the polymer composition of the present embodiment, a diketonato complex represented by the following general formula (1aq) and L 1 A production method 2 of the rare earth complex (1) (hereinafter, also referred to as "Method 2") is provided, which is characterized by reacting with the phosphorus ligand represented by the general formula (3) shown above.

[0085] [Chemical formula]

[0086] (In the formula, R 1 , R 2 , R3 , R 4 , R 5 and X 1 represents the R in the general formula (1), 1 , R 2 , R 3 , R 4 , R 5 and X 1 have the same meaning as above. Ln represents a trivalent rare earth ion. m represents 0, 1 or 2.) L in Method 2 1 can be obtained by the method exemplified in the description of Method 1 above. Commercially available products can also be used.

[0087] In Method 2, it is preferably carried out in a solvent in terms of the good yield of the rare earth complex (1). The solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent include dichloromethane, chloroform, chlorobenzene, methanol, ethanol, propanol, isopropyl alcohol, 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, 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. In terms of the good yield of the rare earth complex (1), chloroform, acetone, methylcyclohexane, methanol, ethanol, toluene or water is preferable.

[0088] Regarding the molar ratio of the diketonato complex (1aq) and the phosphorus ligand (3) in Method 2. It is preferable to use 0.5 mol or more and 5.0 mol or less of L 1 per 1 mol of the diketonato complex (1aq), and it is more preferable to use 1.0 mol or more and 3.0 mol or less of the phosphorus ligand (3a).

[0089] In Method 2, there are no particular restrictions on the reaction temperature and reaction time, and general conditions for producing metal complexes by those skilled in the art can be used. As a specific example, the rare earth complex (1) can be produced with a good reaction yield by selecting a reaction temperature of -80°C or higher and 120°C or lower and a reaction time of 1 minute or longer and 120 hours or shorter.

[0090] The rare earth complex (1) produced by Method 2 can be purified by appropriately selecting and using general purification methods for purifying metal complexes by those skilled in the art. Specific purification methods include one or more selected from the group consisting of filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, precipitation, and column chromatography. [Method for Producing Rare Earth Complex-Containing Polymer Composition] For the rare earth complex-containing polymer composition of this embodiment, as long as the above-described configuration is satisfied, the production method is arbitrary. As a preferred production method, there is a method for producing a rare earth complex-containing polymer composition having a polymerization step of mixing a monomer and the rare earth complex (1) and then polymerizing the rare earth complex-containing monomer to obtain a rare earth complex-containing polymer.

[0091] In the polymerization step, after mixing the monomer and the rare earth complex (1), the monomer is polymerized to obtain a rare earth complex-containing polymer. As a method for mixing the monomer and the rare earth complex (1), there is a method of adding the rare earth complex (1) to the liquid monomer and dissolving the rare earth complex (1) in the monomer by stirring.

[0092] The polymerization method is not particularly limited and can be carried out by known methods such as suspension polymerization and emulsion polymerization. In terms of advantages such as easy reaction control, suspension polymerization is preferred as the polymerization method. Suspension polymerization involves polymerizing the above monomer in water as 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. There is no particular limitation on the radical polymerization initiator, but peroxides are mentioned. For example, at least one of an organic peroxide that generates free radicals by heat and an azo-based initiator can be used.

[0093] The mixing amount of the monomer can be exemplified as 1% by mass or more, 25% by mass or more, or 50% by mass or more with respect to the total mass of the monomer and the rare earth complex (1), and can be exemplified as 99.999% by mass or less, 99.99% by mass or less, or 99.9% by mass or less, and examples 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.

[0094] The mixing amount of the rare earth complex can be exemplified as 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more with respect to the total mass of the monomer and the rare earth complex (1), and can be exemplified as 99% by mass or less, 75% by mass or less, or 50% by mass or less, and examples include 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.

[0095] 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.

[0096] Examples of the azo-based 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.

[0097] The addition amount of the polymerization initiator is not particularly limited, but it can be exemplified that it is 0.01% by mass or more, or 0.1% by mass or more, and further 5% by mass or less, or 2.5% by mass or less, based on 100% by mass of the monomer. Examples 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, based on 100% by mass of the monomer.

[0098] In the polymerization step, it is preferable to mix divinylbenzene. The mixing amount of divinylbenzene can be exemplified that it is 0.01% by mass or more, 0.1% by mass or more, or 0.4% by mass or more, based on the total mass of the monomer and the rare earth complex (1), and further 99% by mass or less, 90% by mass or less, or 75% by mass or less. Examples include 0.01% by mass or more and 99% by mass or less, or 0.4% by mass or more and 75% by mass or less.

[0099] The polymerization of the rare earth complex-containing monomer may be carried out in a solvent. The solvent may be water, and 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.

[0100] When radical polymerizing the monomer, a polymerization inhibitor may be added for the purpose of controlling the volume particle size distribution. The more the polymerization inhibitor is, the more the generation of nanoparticles is suppressed, and there is a tendency to easily obtain a rare earth complex-containing polymer composition with uniform particle size. Examples of the polymerization inhibitor include sodium nitrite, hydroquinone, and potassium hydroquinone sulfonate.

[0101] The rare earth complex-containing polymer obtained by the polymerization step is preferably in a particulate form.

[0102] There are no particular restrictions on the reaction temperature and reaction time in the polymerization process, and those skilled in the art can use general conditions when manufacturing the polymer composition.

[0103] By setting the reaction temperature at 20 °C or higher or 40 °C or higher, a rare earth complex-containing polymer composition can be efficiently produced. Examples of the upper limit of the reaction temperature include 100 °C or lower or 90 °C or lower.

[0104] By setting the reaction time at 30 minutes or longer, 1 hour or longer, or 4 hours or longer, a rare earth complex-containing polymer composition can be efficiently produced. Examples of the upper limit of the reaction time include 72 hours or shorter, 48 hours or shorter, or 24 hours or shorter. Since the degree of polymerization of the resulting polymer composition is likely to increase, the reaction time is preferably 1 hour or longer and 72 hours or shorter, and more preferably 4 hours or longer and 48 hours or shorter.

[0105] The production method of this embodiment may further include a pulverization step of further pulverizing the rare earth complex-containing polymer obtained by the polymerization step. By the pulverization step, a rare earth complex-containing polymer composition with uniform particle size can be obtained. Examples of the pulverization method include mechanical pulverization treatment methods, and one or more selected from the group of ball mill, bead mill, jet mill, and mortar mixing can be mentioned. There is no restriction on the temperature of pulverization, and it may be carried out at normal temperature or by freezing fine particles. In order to suppress the variation in the particle size of the rare earth complex-containing polymer, classification may be performed after the pulverization step. Examples of the classification method include at least either a sieving method or an air classification method, and the sieving method is preferred.

Examples

[0106] Hereinafter, the present disclosure will be described by way of examples. However, the present disclosure is not limited thereto.

[0107] The following analysis methods were used for the identification of the rare earth complex. ( 1 H-NMR, 19 F-NMR and 31 P-NMR) 1 H-NMR, 19 F-NMR and 31 For the measurement of P-NMR, 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 were used. 1 H-NMR was measured using deuterated acetone (Acetone-d 6 ) as the measurement solvent and tetramethylsilane (TMS) as the internal standard substance. 19 F-NMR was measured using deuterated acetone (Acetone-d 6 ) as the measurement solvent. 31 P-NMR was measured using deuterated acetone (Acetone-d 6 ). (Average particle size) The average particle size was obtained by dispersing the rare earth complex-containing polymer composition in pure water, using a particle size distribution measuring device (Microtrac BEL Corporation, Microtrac MT3300EXII), measuring the volume particle size distribution by laser diffraction scattering particle size distribution measurement method under the following conditions, and taking the median diameter obtained as the average particle size.

[0108] Shape of particles: Non-spherical Number of measurements: 3 times Measurement time: 30 seconds Refractive index: 1.49 (Rare earth complex content) The rare earth complex content in the polymer composition was determined by quantifying the rare earth metal content by ICP-AES measurement, converting it to the rare earth complex content, and obtaining the content of the rare earth complex as the mass ratio (% by mass) of the obtained converted content to the mass of the rare earth complex-containing polymer composition. For ICP-AES measurement, 5800 ICP-OES manufactured by Agilent Technologies was used. (Excitation spectrum) Using a spectrophotometer (JASCO Corporation, FP-6500), the measurement was carried out under the following conditions.

[0109] Excitation side slit: 1 nm Fluorescence side slit: 3 nm Emission wavelength: 616 nm (Light resistance test) The emission intensity at 615 nm was measured with a spectrophotometer (manufactured by JASCO Corporation, FP-6500) under the following conditions.

[0110] Excitation side slit: 5 nm Fluorescence side slit: 5 nm Excitation wavelength: 350 nm Next, at room temperature (25 °C), using a UV light irradiator (manufactured by USHIO INC., SP-9) and a lens, UV light of 200 mW / cm 2 (365 nm) was irradiated for the time described in Table 1. The emission intensity of the sample after UV light irradiation was measured again with a spectrophotometer, and the residual ratio of the emission intensity from the initial state was calculated from the following formula to evaluate the light resistance.

[0111] Residual ratio of emission intensity (%) (I / I 0 ) = (Emission intensity at 615 nm after UV light irradiation) / (Emission intensity at 615 nm before UV light irradiation) × 100 (Reference Example 1)

[0112] [Chemical formula]

[0113] Tetrahydrofuran (790 mL) was added to 4-hydroxycoumarin (79.9 g, 493 mmol) and imidazole (101 g, 1.48 mol), and while stirring under ice-cooling, a solution of trifluoroacetic anhydride (69.0 mL, 493 mmol) in tetrahydrofuran (196 mL) was added dropwise. After stirring the reaction solution at room temperature (25 °C) for 4 hours, the solvent was distilled off under reduced pressure, the concentrate was washed 3 times with ethyl acetate, and dried under reduced pressure to obtain a mixture of 4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onatoimidazolium and trifluoroacetic acid imidazolium (molar ratio = 1:0.41) as a white solid (yield 125 g, purity 81.4%, yield 63%). 1H-NMR (400 MHz, Acetone-d 6 ) δ (ppm): 9.72 (brs, 3.0H), 8.98 (dd, J = 1.3, 1.3 Hz, 1.4H), 8.08 (ddd, J = 7.9, 1.7, 0.4 Hz, 1H), 7.71 (d, J = 1.3 Hz, 2.8H), 7.56 (ddd, J = 8.3, 7.2, 1.7 Hz, 1H), 7.22 (ddd, J = 7.9, 7.2, 1.1 Hz, 1H), 7.16 (ddd, J = 8.3, 1.1, 0.4 Hz, 1H). 19 F-NMR (376 MHz, Acetone-d 6 ) δ (ppm): -73.5 (s, 3F), -75.8 (s, 1.2F).

[0114] 42.1 g (99.7 mmol as 5.2 hydrate) of europium(III) acetate hydrate was added to 498 mL of water and 498 mL of toluene, and the mixture was stirred at room temperature (25 °C) for 10 minutes. Then, 77.1 g (199 mmol) of trioctylphosphine oxide was added, and the mixture was further stirred at room temperature (25 °C) for 1 hour. A mixture of 4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onatoimidazolium and imidazolium trifluoroacetate (120 g, molar ratio = 1:0.41, 299 mmol of 4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onatoimidazolium) obtained above was added to the reaction mixture, and the mixture was stirred at room temperature (25 °C) for 2 hours. The layers were separated, and the organic layer was washed twice with 500 mL of water. The solution after washing with water was concentrated under reduced pressure to obtain a colorless oily substance of tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III) (1-5) (yield 164 g, 97% yield). 1 H-NMR (400 MHz, Acetone-d 6) δ (ppm): 7.12 (brs, 3H), 6.90 (brs, 3H), 6.45 ppm (brs, 3H), 6.21 ppm (brs, 3H), 1.43 ppm (brs, 12H), 1.07 - 1.31 ppm (m, 60H), 0.78 - 0.90 ppm (m, 18H), 0.55 ppm (brs, 12H). 19 F - NMR (376 MHz, Acetone - d 6 ) δ (ppm): - 72.2 (s, 9F). 31 P - NMR (162 MHz, Acetone - d 6 ) δ (ppm): - 64.4 (s, 2P).

[0115] (Reference Example 2)

[0116] [Chemical formula]

[0117] 1,3 - Dimethyl - 2 - imidazolidinone (20.0 mL) was added to 2 - naphthol (2.88 g, 20.0 mmol) and cyanoacetic acid (1.70 g, 20.0 mmol), and trifluoroacetic anhydride (11.3 mL, 80.7 mmol) was added dropwise thereto over 2 hours on a water bath at room temperature (25 °C), followed by further stirring for 22 hours. The reaction solution was added to water, and the precipitated solid was collected by suction filtration, washed with water, washed with methanol, and dried in vacuo to obtain 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, yield 44%). 1H - NMR (400 MHz, CDCl3) δ (ppm): 16.50 (brs, 1H), 9.25 (brd, J = 8.8 Hz, 1H), 8.23 (d, J = 8.8 Hz, 1H), 7.95 (brd, J = 8.0 Hz, 1H), 7.80 (ddd, J = 8.8, 7.2, 1.6 Hz, 1H), 7.65 (ddd, J = 8.0, 7.2, 0.9 Hz, 1H), 7.43 (d, J = 8.8 Hz, 1H). 19F - NMR (376 MHz, CDCl3) δ (ppm): - 74.2 (s, 3F).

[0118] Europium acetate n-hydrate (75.0 mg, 204 μmol as the 2.5-hydrate) and triphenylphosphine oxide (111 mg, 399 μmol) were added with methanol (4.00 mL), and the mixture was stirred at room temperature (25 °C) for 1.5 h. 1-Hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-one (185 mg, 600 μmol) obtained above was added to the reaction mixture, and the mixture was stirred at room temperature (25 °C) for 4 h. The reaction solution was poured into water, and the precipitated solid was collected by suction filtration and then washed with water. This solid was suspended in methylcyclohexane, subjected to azeotropic dehydration, then allowed to cool, and the solid was collected by suction filtration to obtain a yellowish-brown 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) (1-3) (yield 183 mg, 56% yield from europium acetate 2.5-hydrate). 19F-NMR (376 MHz, CDCl3) δ (ppm): -71.4 (s, 0.5F), -73.4 (s, 7.3F), -74.0 (s, 1.2F). 31P-NMR (162 MHz, CDCl3) δ (ppm): -80.7 (brs, 0.4P), -81.8 (brs, 1.6P). ESIMS (m / z), MeOH: 1323.1 [M-(1-hydroxy-2-(2,2,2-trifluoroethan-1-one-1-yl)-3H-naphtho[2,1-b]pyran-3-onato)]+. (Comparative Example 1) To an aqueous solution prepared by dissolving a mixture of polyvinyl alcohol (16.0 g) and sodium nitrite (102 mg, 1.47 mmol) in pure water (800 mL), a mixture of methyl methacrylate monomer (80.0 g, 800 mmol), divinylbenzene (meta, para mixture) (419 mg, 3.22 mmol), 2,2' - azobisisobutyronitrile (1.60 g, 9.74 mmol), and bis(tricyclohexylphosphine oxide)tris(hexafluoroacetylacetonato)europium(III) (405 mg, 0.293 mmol) was added. After suspending this mixture by stirring for 30 minutes, it was stirred at 75 °C for 6 hours. The resulting white suspension was filtered and washed with pure water. By drying this under reduced pressure with heating, a polymer composition (21.8 g) containing bis(tricyclohexylphosphine oxide)tris(hexafluoroacetylacetonato)europium(III) was obtained. (Example 1) To an aqueous solution prepared by dissolving polyvinyl alcohol (10.0 g) and potassium hydroquinonesulfonate (0.791 g, 3.47 mmol) in pure water (788 mL), a mixture of methyl methacrylate monomer (200 g, 2.00 mol), divinylbenzene (meta, para mixture) (1.01 g, 7.79 mmol), 2,2'-azobis(2,4-dimethylvaleronitrile) (4.01 g, 16.1 mmol), and tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III) (1.01 g, 0.595 mmol) obtained in Reference Example 1 was added. After suspending this mixture by stirring for 30 minutes, it was stirred at 80 °C for 2 hours. The resulting white suspension was filtered and washed with pure water. It was further washed with ethanol, and after removing the supernatant by decantation, it was dried under reduced pressure with heating (70 °C, 66 hours) to obtain polymer microparticles (181 g) containing tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III). This was pulverized with a ball mill for 1 hour and classified to obtain 14.9 g of a polymer composition containing 0.32% by mass of tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide) europium(III) with an average particle diameter of 9.7 μm. (Example 2) To an aqueous solution prepared by dissolving polyvinyl alcohol (10.0 g) and sodium nitrite (0.790 g, 11.4 mmol) in pure water (787 mL), a mixture of methyl methacrylate monomer (200 g, 2.00 mol), divinylbenzene (meta, para mixture) (1.01 g, 7.73 mmol), 2,2'-azobis(2,4-dimethylvaleronitrile) (4.00 g, 16.1 mmol), and tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide) europium(III) (10.8 g, 6.37 mmol) obtained in Reference Example 1 was added. The mixture was suspended by stirring for 30 minutes, then stirred at 80 °C for 6.5 hours. After returning the resulting white suspension to room temperature (25 °C), it was centrifugally sedimented at 5250 G for 8 minutes, and the supernatant was removed by decantation. Pure water (1 L) was added to the obtained white cake, and it was stirred for 5 minutes, then centrifugally sedimented at 5250 G for 8 minutes, and the supernatant was removed. This operation was repeated 2 more times. Ethanol (1 L) was added to the obtained white cake, and it was stirred for 4 minutes, then centrifugally sedimented at 5250 G for 4 minutes, and the supernatant was removed by decantation. After repeating this 1 more time, it was dried by heating under reduced pressure (50 °C, 23 hours) to obtain 184 g of polymer fine particles containing 5.1% by mass of tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide) europium(III) with an average particle diameter of 7.5 μm. (Example 3) A polymer fine particle (181 g) containing 5.3 mass% of tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III) with an average particle diameter of 7.5 μm was obtained under the same conditions as in Example 2, except that methyl methacrylate monomer was 180 g (1.80 mol) and divinylbenzene (meta, para mixture) was 20.0 g (154 mmol). (Example 4) A polymer fine particle (162 g) containing 4.8 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) with an average particle diameter of 8.2 μm was obtained under the same conditions as in Example 2, except that 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) (10.8 g, 6.63 mmol) obtained in Reference Example 2 was used instead of tris[4-hydroxy-3-(2,2,2-trifluoroethan-1-one-1-yl)-2H-chromen-2-onato]bis(trioctylphosphine oxide)europium(III).

[0119] The evaluation results of the light resistance tests of Examples 1 to 4 are shown in Table 1.

[0120]

Table 1

[0121] The rare earth complex-containing polymer composition of this example has a high emission intensity retention rate after an accelerated degradation test by ultraviolet irradiation, emits strongly when excited by ultraviolet light with a wavelength of 300 nm or more and 380 nm or less, and it was confirmed that it is a polymer composition excellent in both light resistance and wavelength conversion function for near-ultraviolet light. Also, it was confirmed that the rare earth complex-containing polymer composition of Example 2 has a higher degree of polymerization than the rare earth complex-containing polymer composition of Example 1, and thus has a higher emission intensity retention rate. Furthermore, it was confirmed that the rare earth complex-containing polymer composition of Example 3 has a higher degree of crosslinking than the rare earth complex-containing polymer composition of Example 2, and thus has a higher emission intensity retention rate. On the other hand, it was confirmed that the polymer composition of this comparative example has a weak emission intensity when excited by ultraviolet light with a wavelength of 360 nm or more, and is a polymer composition with poor wavelength conversion function for near-ultraviolet light.

Claims

1. A rare earth complex-containing polymer composition comprising a rare earth complex represented by general formula (1) and one or more polymers selected from the group consisting of polymethyl methacrylate, polybutyl methacrylate, a fluorine-containing acrylic resin, and polystyrene, and having an average particle size of 5 μm or more and 150 μm or less. 【Chemistry 1】 [In the formula, R １ R represents a haloalkyl group having 1 to 6 carbon atoms. ２ , R ３ , R ４ and R ５ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms which may be substituted with an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms which may be substituted with a halogen atom. Also, R ２ , R ３ , R ４ and R ５ Among these, two adjacent substituents may be bonded together with the benzene ring to form a 5-, 6-, or 7-membered ring. [In the formula, X １ each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group represented by the following general formula (2). 【Chemistry 2】 (In the formula, X ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 4 to 12 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halocycloalkyl group having 3 to 6 carbon atoms, or a haloalkyloxy group having 1 to 6 carbon atoms, the aryl group being optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkyloxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, and a nitro group. Ln represents a trivalent rare earth ion.

2. 2. The rare earth complex-containing polymer composition according to claim 1, wherein Ln is europium ion (III).

3. R ２ , R ３ , R ４ and R ５ The rare earth complex-containing polymer composition according to claim 1 or 2, wherein each of the is a hydrogen atom.

4. 3. A method for producing a rare earth complex-containing polymer composition according to claim 1, comprising: a polymerization step of mixing a monomer with the rare earth complex (1) and polymerizing the monomer to obtain polymer fine particles; and a pulverization step of pulverizing the polymer fine particles.

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