resin composition

Abstract

To provide a new resin composition that is colored and has fluorescence.SOLUTION: A resin composition contains a rare earth complex, and a resin. The rare earth complex contains one rare earth ion, and a plurality of ligands coordinated to the rare earth ion. At least one of the plurality of ligands is a diketone ligand. At least one of the plurality of ligands includes a chromophore that gives the rare earth complex a maximum absorption wavelength in a wavelength region of 400-600 nm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition. [Background technology]

[0002] Resin compositions containing rare earth complexes have been investigated for use in various applications such as light-emitting materials (for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-15564 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-4893 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-15894 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one aspect of the present invention is to provide a new resin composition that is colored and has fluorescent properties. [Means for solving the problem]

[0005] One aspect of the present invention relates to a resin composition comprising a rare earth complex and a resin, wherein the rare earth complex comprises one rare earth ion and a plurality of ligands coordinated to the rare earth ion, at least one of the plurality of ligands being a diketone ligand, and at least one of the plurality of ligands having a chromophore that imparts a maximum absorption wavelength to the rare earth complex in the wavelength range of 400 to 600 nm. The resin composition of the present invention is colored and fluorescent because it contains the rare earth complex.

[0006] The chromophore in the rare earth complex in the resin composition may have a pyrromethene skeleton or a merocyanine skeleton, which makes the rare earth complex colored in the solid state or in solution under visible light and further improves the fluorescent properties of the rare earth complex.

[0007] At least one of the plurality of ligands in the rare earth complex in the resin composition may be a phosphine oxide ligand having a chromophore.

[0008] The phosphine oxide ligand having a chromophore may be a ligand represented by the following formula (III): In this case, the rare earth complex is colored in the solid state or in solution under visible light, and the fluorescence emission properties of the rare earth complex are further improved. [ka] [In the formula, X 11 and X 12 are each independently an aromatic group, a heteroaromatic group, or C 1~12 Alkyl group, C 3~12 Alkenyl group, C 3~12 Cycloalkyl groups, C 3~12 Cycloalkenyl group, C 3~12 Alkynyl groups, aromatic oxy groups, heteroaromatic oxy groups, C 1~12 Alkyloxy group, C 3~12 Alkenyloxy group, C 3~12 Cycloalkyloxy group, C 3~12 cycloalkenyloxy group, or C 3~12 represents an alkynyloxy group represented by the formula: Z 1 represents a group represented by the following formula (I) or (II). [ka] (In formula (I), n and m represent integers of 0 to 3, L 1represents a divalent organic group, an alkylene group, or a phenylene group containing a first bonding group, wherein the first bonding group is at least one selected from the group consisting of a carbonyl group (-C(=O)-), an ester group (-COO-), an amide group (-NH-C(=O)-), an ether group (-O-), and a thioether group (-S-); R 11 and R 12 each independently represent a monovalent organic group containing a second bonding group, an alkyl group, a cyano group, a hydroxy group, a nitro group, a sulfo group, an amino group, a silyl group, a phosphonic acid group, a diazo group, a mercapto group, or a halogen atom, and the second bonding group is at least one selected from the group consisting of a carbonyl group, an ester group, an ether group, and a thioether group; If m is 2 or more, there are multiple R 11 may be the same or different, and when n is 2 or more, a plurality of R 12 may be the same or different.) [ka] (In formula (II), p represents an integer of 0 to 4; R 21 represents a monovalent organic group containing a third bonding group, an alkyl group, a cyano group, a hydroxy group, a nitro group, a sulfo group, an amino group, a silyl group, a phosphonic acid group, a diazo group, a mercapto group, or a halogen atom, and the third bonding group is at least one selected from the group consisting of a carbonyl group, an ester group, an ether group, and a thioether group; R 22 ~R 25 are each independently, C 1-12 represents an alkyl group, L 3 represents an alkylene group or an arylene group, If p is 2 or more, there are multiple R 21 may be the same or different.)]

[0009] The rare earth ions in the rare earth complex in the resin composition may be Eu ions or Tb ions, in which case the rare earth complex will have even better fluorescent properties. [Effects of the Invention]

[0010] According to one aspect of the present invention, a new resin composition that is colored and has fluorescent properties can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows the results of X-ray crystal structure analysis of (Z)-5-(2-((E)-1,3,3-trimethylindolin-2-ylidene)ethylidene)-1-(3-(diphenylphosphoryl)propyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile. [Figure 2] FIG. 1 is a diagram showing the results of measuring the absorption wavelength of an Eu complex in an example. [Figure 3] FIG. 1 shows the results of measuring the excitation wavelength of an Eu complex in an example. [Figure 4] FIG. 1 is a diagram showing the measurement results of the fluorescence wavelength of an Eu complex in an example. [Figure 5] FIG. 10 is a diagram showing the results of measuring the absorption wavelength of a Eu complex in a comparative example. [Figure 6] FIG. 10 is a diagram showing the measurement results of the excitation wavelength of a Eu complex in a comparative example. [Figure 7] FIG. 10 is a diagram showing the measurement results of the fluorescence wavelength of a Eu complex in a comparative example. [Figure 8] FIG. 1 is a diagram showing the results of measuring the absorption wavelength of a resin composition containing an Eu complex in an example. [Figure 9] FIG. 1 is a diagram showing the results of measuring the fluorescence wavelength of a resin composition containing an Eu complex in an example. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0013] [Resin composition] One embodiment of the present invention is a resin composition comprising a rare earth complex and a resin. The rare earth complex comprises one rare earth ion and a plurality of ligands coordinated to the rare earth ion, at least one of which is a diketone ligand, and at least one of which has a chromophore that gives the rare earth complex a maximum absorption wavelength in the wavelength range of 400 to 600 nm. Due to this characteristic, the rare earth complex is excited by light in the ultraviolet range and exhibits fluorescence in the visible range, and also exhibits a clear color in the visible range that does not include light in the ultraviolet range.

[0014] The resin composition according to the present embodiment contains the rare earth complex, and therefore is colored in the visible light region and has fluorescent properties. Furthermore, in a resin composition using this rare earth complex as a dye, it is not necessary to use two compounds with different solubilities, a rare earth complex that is excited only in the ultraviolet region and an organic dye that absorbs in the visible region, and dyeing can be performed with a single component, making it easier to impart functionality.

[0015] Examples of resins include polymethyl (meth)acrylate, polycarbonate, polystyrene, polyurethane, polycarbonate, polyester, polyether, polyamide, polyvinyl chloride, silicone, epoxy resin, fluorine-based resin, polyethylene, polypropylene, etc. The resin may be a copolymer combining various monomers or a mixture of multiple resins.

[0016] The resin may be in the form of a film, sheet, fiber, fabric, paper, particles, pellets, or liquid.

[0017] The rare earth ion in the rare earth complex is a divalent to tetravalent rare earth ion, and may be a divalent or trivalent rare earth ion. The rare earth ion may be, for example, an ion of a lanthanide series element such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu. From the viewpoint of further improving the fluorescence emission property, the rare earth ion may be an Eu ion or a Tb ion.

[0018] At least one of the plurality of ligands coordinated to the rare earth ion is a diketone ligand (β-diketone ligand). By having the diketone ligand, the rare earth complex can have good fluorescent emission properties. The rare earth ion may be coordinated with a ligand other than the diketone ligand. The ligand other than the diketone ligand may be, for example, a phosphine oxide ligand.

[0019] At least one of the ligands has a chromophore that gives the rare earth complex a maximum absorption wavelength in the wavelength range of 400 to 600 nm. This wavelength range may be, for example, 450 to 550 nm. The presence of the above-mentioned chromophore in at least one of the ligands in the rare earth complex can be confirmed by measuring the absorbance of the rare earth complex and determining the maximum absorption wavelength of the rare earth complex. The absorbance of the rare earth complex can be measured under the conditions described in the Examples below.

[0020] From the viewpoint of further improving the fluorescence of the rare earth complex moiety, it is preferable that the chromophore has low absorption in the ultraviolet region with wavelengths less than 400 nm. The reason for this is that the fluorescence process of the rare earth complex begins with the diketone ligand absorbing light in the ultraviolet region of 300 to 400 nm and becoming excited. From there, energy transfer occurs to the rare earth metal center, resulting in the fluorescence of the rare earth complex. Therefore, it is required that the ligand having the chromophore does not affect the fluorescence of the rare earth complex. Therefore, it is preferable that the absorption at wavelengths less than 400 nm is as small as possible.

[0021] The molar absorption coefficient of the rare earth complex at the maximum absorption wavelength in the wavelength range of 400 to 600 nm may be, for example, 1000 or more or 5000 or more, or may be, for example, 200000 or less.

[0022] The ligand having a chromophore may be a compound having a coordinating group that forms a coordinate bond with a rare earth ion and a group containing a chromophore. The coordinating group of the ligand having a chromophore may be, for example, a phosphine oxide group or a β-diketonato group. The ligand having a chromophore may be a monodentate or bidentate ligand. The number of groups containing a chromophore in one molecule may be, for example, 1 to 5, or may be 1. When one molecule contains multiple chromophores, the chromophores may be the same or different.

[0023] The chromophore may have a dye skeleton that exhibits sufficiently low absorption of light with wavelengths of less than 400 nm, for example, at least one skeleton selected from the group consisting of a pyrromethene skeleton (e.g., a boron dipyrromethene skeleton) and a merocyanine skeleton. Chromophores having the above skeletons exhibit sufficiently low absorption of light with wavelengths of less than 400 nm, which is necessary for exciting rare earth complexes. Therefore, rare earth complexes containing the above chromophores exhibit sufficient coloring properties and even better fluorescent properties. Resin compositions containing such rare earth complexes are sufficiently colored and have even better fluorescent properties.

[0024] The ligand having a chromophore containing a pyrromethene skeleton (boron dipyrromethene skeleton) may contain, for example, a group containing a chromophore represented by the following formula (I): When the chromophore represented by the following formula (I) is contained, the rare earth complex can have coloring properties and superior fluorescent properties. [ka]

[0025] In formula (I), * represents a bond, and n and m each independently represent an integer of 0 to 3. n and m may be 0 to 2, 0 to 1, or 0.

[0026] R 11 and R 12 R each independently represents a monovalent organic group containing a second bonding group, an alkyl group, a cyano group (-CN), a hydroxyl group (-OH), or a halogen atom. The second bonding group may be at least one selected from the group consisting of a carbonyl group (-C(=O)-), an ester group (-COO-), an ether group (-O-), and a thioether group (-S-). 11 and R 12 The number of carbon atoms in the alkyl group represented by the formula (I) may be, for example, 1 to 20, 1 to 15, 1 to 10, or 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The halogen atom may be, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. When m is 2 or more, a plurality of R 11 may be the same or different, and when n is 2 or more, a plurality of R 12 may be the same or different.

[0027] L 1 represents a divalent organic group, alkylene group, or phenylene group containing a first bonding group. The first bonding group may be at least one selected from the group consisting of a carbonyl group (-C(=O)-), an ester group (-COO-), an amide group (-NH-C(=O)-), an ether group (-O-), and a thioether group (-S-). 1 may be, for example, an alkylene group containing a first bonding group, an arylene group (e.g., a phenylene group) containing a first bonding group, or a group consisting of a first bonding group, an alkylene group, and an arylene group. The group represented by formula (I) may be bonded to a coordinating group via an ether group (-O-) or a thioether group (-S-).

[0028] The group represented by formula (I) may be, for example, a group represented by the following formula (Ia): [ka]

[0029] In formula (Ia), m, n, R 11 , R 12 and * are as defined above. o is an integer of 0 to 4. o may be 0 to 3, 0 to 2, 0 to 1, or 0. R 13 R represents a monovalent organic group containing a fourth linking group, an alkyl group, a cyano group, a hydroxy group, a nitro group, a sulfo group, an amino group, a silyl group, a phosphonic acid group, a diazo group, a mercapto group, or a halogen atom. The fourth linking group may be at least one selected from the group consisting of a carbonyl group, an ester group, an ether group, and a thioether group. 13 A specific example of this is the above R 11 and R 12 It may be similar to:

[0030] L 2 represents an alkylene group or an arylene group. 2 The number of carbon atoms in the alkylene group represented by the formula (L) may be, for example, 1 to 12, 1 to 10, or 1 to 6. 2 The alkylene group represented by the formula (L) may be, for example, a methylene group (—CH—), an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. 2 The arylene group represented by the formula (I) may be, for example, a phenylene group (—C 6 H 4 —) or a naphthylene group.

[0031] In the group represented by formula (I), m, n, and o are 0, and L 2 is a methylene group, and may be a group represented by the following formula (Ib): [ka]

[0032] The ligand having a chromophore containing a merocyanine skeleton may contain, for example, a group containing a chromophore represented by the following formula (II): When the chromophore represented by the following formula (II) is contained, the rare earth complex can have coloring properties and superior fluorescent properties. [ka]

[0033] In formula (II), p represents an integer of 0 to 4. p may be 0 to 3, 0 to 2, 0 to 1, or 0. * represents a bond.

[0034] R 21 represents a monovalent organic group containing a third linking group, an alkyl group, a cyano group, a hydroxy group, a nitro group, a sulfo group, an amino group, a silyl group, a phosphonic acid group, a diazo group, a mercapto group, or a halogen atom. The third linking group may be at least one selected from the group consisting of a carbonyl group, an ester group, an ether group, and a thioether group. When p is 2 or more, a plurality of R 21 may be the same or different. 21 The details of the substituents represented by R 11 and R 12 may be the same as the substituent represented by the following formula:

[0035] R 22 ~R 25 are each independently, C 1-12 Indicates an alkyl group. 22 ~R 25 C, represented by 1-12 The alkyl group is an alkyl group having 1 to 12 carbon atoms. 22 ~R 25 For example, C 1-12 Alkyl groups, C 1-6 Alkyl group or C having 1 to 6 carbon atoms 1-6 It may be an alkyl group. 1-12 The alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

[0036] L 3 represents an alkylene group or an arylene group. 3 The details of the alkylene group and arylene group represented by the formula (I) may be as described above.

[0037] The group represented by formula (II) is a group in which p is 0 and R 22 ~R 25 is a methyl group, and L3 is an n-propylene group (—CH2—CH2—CH2—), the rare earth complex can have coloring properties and superior fluorescent properties. [ka]

[0038] At least one of the plurality of ligands may be a phosphine oxide ligand having the above-mentioned chromophore. That is, at least one of the plurality of ligands in the rare earth complex may be a phosphine oxide ligand having a chromophore represented by the following formula (III). In this case, the rare earth complex can have coloring properties and superior fluorescent properties. [ka]

[0039] Z 1 represents a group containing the above chromophore, for example, a group represented by formula (I) or (II).

[0040] X 11 and X 12 are each independently an aromatic group, a heteroaromatic group, or C 1~12 Alkyl group, C 3~12 Alkenyl group, C 3~12 Cycloalkyl groups, C 3~12 Cycloalkenyl group, C 3~12 Alkynyl groups, aromatic oxy groups, heteroaromatic oxy groups, C 1~12 Alkyloxy group, C 3~12 Alkenyloxy group, C 3~12 Cycloalkyloxy group, C 3~12 cycloalkenyloxy group, or C 3~12 represents an alkynyloxy group of the formula:

[0041] The aromatic group may be a phenyl group, a naphthyl group, a biphenyl group, etc. The heteroaromatic group may be a pyrrolyl group, a furalyl group, an indolyl group, a thienyl group, etc. At least a portion of the hydrogen atoms bonded to these groups may be substituted with other groups, and may have at least one substituent selected from the group consisting of, for example, a hydroxy group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, a mercapto group, and a halogen atom.

[0042] C 1~12 The alkyl group is an alkyl group having 1 to 12 carbon atoms. 1~12 Alkyl group (C n H 2n+1 (n=1 to 12) may be linear or branched. 1~12 At least one hydrogen atom of the alkyl group may be substituted with another group, or may not be substituted. 1~12 The alkyl group may be, for example, a perfluoroalkyl group (C n F 2n+1 : n = 1 to 12) and perchloroalkyl groups (C n Cl 2n+1 : n = 1 to 12) and other linear or branched C 1~12 Examples of the alkyl group having a substituent include aralkyl groups such as a benzyl group and a phenethyl group, and perhalogenated aralkyl groups such as a perfluorobenzyl group.

[0043] C 3~12 The alkenyl group is an alkenyl group having 3 to 12 carbon atoms. 3~12 The alkenyl group may be straight-chained or branched. 3~12 Examples of the alkenyl group include an allyl group and a butenyl group. 3~12 At least one hydrogen atom of the alkenyl group may be substituted with another group, or may be unsubstituted. 3~12The alkenyl group may be, for example, a linear or branched C alkyl group, such as a perfluoroalkenyl group and a perchloroalkenyl group, for example, a perfluorovinyl group, a perfluoroallyl group, and a perfluorobutenyl group. 3~12 Examples include perhalogenated alkenyl groups.

[0044] C 3~12 The cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms. 3~12 The alkenyl group may be straight-chained or branched. 3~12 At least one hydrogen atom of the cycloalkyl group may be substituted with another group, or may be unsubstituted. 3~12 The cycloalkyl group may be, for example, a perfluorocycloalkyl group (C n F 2n-1 : n = 3 to 12) and perchlorocycloalkyl groups (C n Cl 2n-1 :n=3~12) etc. 3~12 Perhalogenated cycloalkyl groups are included.

[0045] C 3~12 The cycloalkenyl group is a cycloalkenyl group having 3 to 12 carbon atoms. 3~12 Examples of the cycloalkenyl group include a cyclopentenyl group and a cyclohexenyl group. 3~12 At least one hydrogen atom of the cycloalkenyl group may be substituted with another group, or may be unsubstituted. 3~12 The cycloalkenyl group is, for example, a C cycloalkenyl group such as a perfluorocycloalkenyl group or a perchlorocycloalkenyl group. 3~12 It may be a perhalogenated cycloalkenyl group.

[0046] C 3~12 The alkynyl group is an alkynyl group having 3 to 12 carbon atoms. 3~12 At least one hydrogen atom of the alkynyl group may or may not be substituted with another group.

[0047] The aromatic oxy group is a group in which the above aromatic group is bonded to an oxy group (—O—). The heteroaromatic oxy group is a group in which the above heteroaromatic group is bonded to an oxy group. 1~12 The alkyloxy group is the C 1~12 A group formed by bonding an alkyl group and an oxy group. C 3~12 The alkenyloxy group is the C 3~12 It is a group formed by bonding an alkenyl group and an oxy group. 3~12 The cycloalkyloxy group is the C 3~12 A group formed by bonding a cycloalkyl group and an oxy group. 3~12 The cycloalkenyloxy group is the C 3~12 A group formed by bonding a cycloalkenyl group and an oxy group. 3~12 The alkynyloxy group of the above C 3~12 is a group in which an alkynyl group and an oxy group are bonded together.

[0048] X 11 and X 12 The above group represented by the formula (I) may have one or more -COO- and -CO- inserted between the C-C single bonds at any position.

[0049] X 11 and X 12 may each independently be an aromatic group or a phenyl group.

[0050] Specifically, the ligand having a chromophore may be a compound represented by the following formula (A-1) or (A-2): In this case, the rare earth complex can have coloring properties and superior fluorescent properties. [ka] [ka]

[0051] The rare earth complex according to this embodiment may be, for example, a complex represented by the following formula (IV). [ka]

[0052] In the formula, Ln represents a rare earth element, n1 represents an integer of 2 to 4, n2 represents an integer of 2 to 4, and n3 represents an integer of 0 to 2.

[0053] X 21 , X 22 and X 23 are each independently an aromatic group, a heteroaromatic group, or C 1~12 Alkyl group, C 3~12 Alkenyl group, C 3~12 Cycloalkyl groups, C 3~12 Cycloalkenyl group, C 3~12 Alkynyl groups, aromatic oxy groups, heteroaromatic oxy groups, C 1~12 Alkyloxy group, C 3~12 Alkenyloxy group, C 3~12 Cycloalkyloxy group, C 3~12 Cycloalkenyloxy group, C 3~12 represents an alkynyloxy group or a group containing a chromophore.

[0054] Y 1 and Y 2 are each independently an aromatic group, a heteroaromatic group, or C 1~12 Alkyl group, C 3~12 Alkenyl group, C 3~12 Cycloalkyl groups, C 3~12 Cycloalkenyl group, C 3~12 The heteroaromatic group includes an alkynyl group or a group containing a chromophore. Examples of the heteroaromatic group include a thiophenyl group.

[0055] X 21 , X 22 , X 23 , Y 1 and Y 2 C 1~12 Alkyl group, C 3~12 Alkenyl group, C 3~12 Cycloalkyl groups, and C 3~12In the cycloalkenyl group, some or all of the hydrogen atoms may be substituted with halogen atoms, such as fluorine atoms or chlorine atoms.

[0056] X 21 , X 22 , X 23 , Y 1 and Y 2 Specific examples of the substituent represented by the formula may be as described above.

[0057] Y 3 represents a hydrogen atom or a deuterium atom.

[0058] If n3 is 0, then Y 1 and Y 2 At least one of the groups is a group containing a chromophore. When n3 is 1 or 2, X 21 , X 22 , X 23 , Y 1 and Y 2 At least one or any one of the groups is a group containing a chromophore.

[0059] The rare earth complex can be incorporated into the resin composition by the following methods: For example, several methods can be selected, such as a method of impregnating a film, fibrous, or particulate object with a solution containing the rare earth complex and drying the resulting solution, a method of dissolving the rare earth complex and resin in an organic solvent and applying the solution to a substrate using various coating techniques and drying the resulting solution, a method of adding a dye solution to a resin dispersion to dye the resin, or a method of directly adding the rare earth complex during melt-kneading of resin pellets.

[0060] The content of the rare earth complex in the resin composition is appropriately selected depending on the purpose of the resin composition. For example, the content of the rare earth complex in the resin composition may be 0.001 parts by mass or more, or 0.01 parts by mass or more, and 0.5 parts by mass or less, or 0.4 parts by mass or less, per part by mass of the resin.

[0061] The content of the resin may be adjusted appropriately depending on the application, required properties, etc. of the resin composition. The content of the resin in the resin composition may be 50% by mass or more or 60% by mass or more, and may be 99.9% by mass or less, or 99% by mass or less, based on the total mass of the resin composition.

[0062] The resin composition may contain an inorganic substance inside and / or within the resin. Examples of the inorganic substance include ceramic fillers such as silica, alumina, silicon nitride, and boron nitride, and metal particles such as iron, nickel, and cobalt.

[0063] The resin composition may further contain other components, such as additives such as antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, lubricants, plasticizers, antistatic agents, thixotropic agents, surfactants, thickeners, inorganic fillers, and pigments.

[0064] The resin composition can be used, for example, for dyeing plastic raw materials, coating materials such as paints, printing inks, and paint materials, writing implements such as paints and pens, toys, resins for 3D printers, agricultural films, display plates for safety, disaster prevention, and crime prevention products, fluorescent labeling agents for biomolecules such as proteins and nucleic acids, and labeling agents for immunoassay methods.

[0065] [Method for producing resin composition] The resin composition can be produced by a method including a step of mixing a resin and a rare earth complex.

[0066] The rare earth complex can be produced by a method including a step of reacting a complex precursor containing a rare earth ion with a ligand having a chromophore to coordinate the ligand having a chromophore to the rare earth ion. The reaction may be carried out under heating. Specific examples of reaction conditions may be as described in the Examples below.

[0067] The ligand having a chromophore can be produced according to a conventional synthesis method, and examples of the synthesis method for the ligand having a chromophore will be shown in the examples below.

[0068] For example, a ligand compound having a chromophore (compound B) represented by formula (B) can be synthesized according to the following reaction scheme. [ka]

[0069] Compound B can be obtained, for example, by a method including the steps of reacting a compound represented by formula (1) (compound 1), ethyl cyanoacetate, a compound represented by formula (2) (compound 2), and a base to obtain a compound represented by formula (3) (compound 3), and reacting compound 3, a compound represented by formula (4) (compound 4), and acetic anhydride to obtain compound B.

[0070] In the formula, X 31 and X 32 is X in formula (IV) 21 and X 22 q has the same meaning as p in formula (II). 31 ~R 35 is R in formula (II) 21 ~R 25 R 36 R represents a hydrocarbon group such as an alkyl group. 31 may be, for example, a methyl group or an ethyl group.

[0071] Compound 1 can be produced according to a conventional synthesis method. Examples of the synthesis method for Compound 1 are as described in the Examples below.

[0072] The reaction to obtain compound 3 is usually carried out in the presence of a base. The base may be, for example, piperidine, pyridine, triethylamine, and / or hexamethyleneimine. The reaction to obtain compound 3 may be carried out in the presence of a solvent. Examples of the solvent include ethanol, dichloromethane, tetrachloroethane, carbon tetrachloride, diethyl ether, tetrahydrofuran, benzene, and toluene. The reaction to obtain compound 3 may be carried out under heating. After completion of the reaction, post-treatment may be carried out by a conventional method. Specific examples of reaction conditions are as described in the Examples below.

[0073] Compound 3 is useful as a precursor compound of compound B. Another embodiment of the present invention is a compound represented by formula (3). In the compound represented by formula (3), R 35 is C 1-10 may be an alkyl group, 1-6 It may be an alkyl group or a methyl group. 4 may be an alkylene group, for example, an n-propylene group. The compound represented by formula (3) may specifically be a compound represented by the following formula (3-1). [ka] [Example]

[0074] The present invention will be described in more detail below based on examples, but is not limited to the following examples. In the following description, "TTA" is an abbreviation for thenoyltrifluoroacetone, and "TOPO" is an abbreviation for trioctylphosphine oxide.

[0075] <Ligand synthesis 1> Synthesis Example 1-1: Synthesis of (3-aminopropyl)diphenylphosphine oxide [ka]

[0076] 3.8 mol of 3-chloropropylamine hydrochloride was added with 10 mL of dry benzene and 5 mL of chloroform, respectively. Then, 8.3 mmol of triethylamine solution (dissolved in 3.3 mL of dry benzene and 1.7 mL of chloroform) was added. After stirring for 20 minutes, the mixture was cooled to 2-4°C and 3.8 mmol of diphenylchlorophosphine was added. oxide A solution (dissolved in 6.6 mL of dry benzene and 3.4 mL of chloroform) was added. After stirring for 1 hour, the temperature was raised to reflux and stirred for another 1 hour. The temperature was lowered to room temperature, and the solvent was distilled off. The residue was dissolved in 50 mL of chloroform and extracted with 100 mL of distilled water. The organic layer was removed, and an aqueous sodium hydroxide solution was added until the pH reached 10, followed by extraction with 100 mL of chloroform. The chloroform was distilled off, and the target compound represented by the above formula (1-1) was obtained. The yield was 75%.

[0077] Synthesis Example 1-2: 1-(3- ( Synthesis of (diphenylphosphoryl)propyl)-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ka]

[0078] To 1 mmol of the compound represented by formula (1-1), 1 mmol of ethyl cyanoacetate and 5 mL of ethanol were added and stirred at room temperature for 6 hours. Then, 1.1 mmol of ethyl acetoacetate and 0.1 mL of piperidine were added and stirred at 110°C. After cooling to room temperature, the solvent was distilled off and 10 mL of 10% hydrochloric acid was added. The resulting precipitate was collected by filtration, washed with distilled water and hexane, and then dried to obtain the compound represented by formula (1-2) as the target product. The yield was 65%.

[0079] Synthesis example 1-3: (Z)-5-(2-((E)- 1,3,3-trimethyl Synthesis of (indolin-2-ylidene)ethylidene)-1-(3-(diphenylphosphoryl)propyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile [ka]

[0080] To 1 mmol of the compound represented by the above formula (1-2), 1.05 mmol of 2-(1,3,3-trimethylindolin-2-ylidene)acetaldehyde and 3 mL of acetic anhydride were added and refluxed for 15 minutes. The resulting precipitate was collected by filtration, washed with hexane, and dried to obtain the compound represented by the above formula (1-3). The yield was 82%. 31 P-NMR: 32.4 ppm (solvent: chloroform)

[0081] The compound represented by formula (1-3) was confirmed to have been obtained by X-ray crystal structure analysis. The results of the X-ray crystal structure analysis are shown in Figure 1. Measurements were performed using a D8 VENTURE, and analysis was performed using a VESTA.

[0082] <Synthesis of Rare Earth Complexes in Examples> Synthesis Example 1-4: Synthesis of Eu complexes of the examples [ka]

[0083] 1 mmol of the compound represented by formula (1-3) was added to 1 mmol of Eu(TTA)3·2H2O and 10 mL of isopropanol, and the mixture was refluxed at 80°C for 4 hours. The solvent was then distilled off to obtain the target Eu complex of this example. The yield was 87%. 31 P-NMR: -93.1 ppm (solvent: chloroform), nanoESI-MS: 1414.1064 (C 59 H 46 O9N3F9PS3Eu+Na + , theoretical value: 1414.1095)

[0084] <Ligand synthesis 2> Synthesis Example 2-1: Synthesis of 4-(5,5-difluoro-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)benzyl diphenylphosphinate [ka] 1.5 mmol of (4-(5,5-difluoro-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-10-yl)phenyl)methanol was dissolved in 30 mL of dichloromethane, and 1.0 mmol of chlorodiphenylphosphine oxide and 3.0 mmol of pyridine were added, followed by stirring at 40°C for 8 hours. The solvent was evaporated, and the residue was purified by column chromatography to obtain the target product in a yield of 63%.

[0085] <Synthesis of Rare Earth Complexes of Comparative Examples> Comparative synthesis example: Synthesis of Eu(TTA)3·(TOPO)2 [ka]

[0086] 1 mmol of Eu(TTA)3·2H2O and 2 mmol of TOPO (trioctylphosphine oxide) were added to 10 mL of ethanol and stirred at room temperature. The solvent was distilled off to obtain the target product. The product was purified by recrystallization using ethanol and distilled water. This yielded the Eu complex (Eu(TTA)3·(TOPO)2) of the comparative example. The yield was 78%. 31 P-NMR: -49.8 ppm (solvent: chloroform), nanoESI-MS: 1611.6082 (C 72 H 114 O8F9P2S3Eu+Na + , theoretical value: 1611.6117)

[0087] evaluation 0.35 mmol of the Eu complex was dissolved in 10 mL of chloroform, and the solution was diluted 1000 times to prepare a measurement sample.

[0088] Absorption wavelength was measured using a Jasco V-650 spectrophotometer. Excitation wavelength and fluorescence wavelength were measured using a Hitachi High-Tech F-7000 with a long-pass filter: LPF-39, and photoluminescence intensity (PL intensity) was measured. A square cell (10 mm square, quartz) was used for measurements. The excitation wavelength was set to 615 nm as the monitor wavelength. The fluorescence wavelength was set to 350 nm as the excitation wavelength.

[0089] The measurement results of the absorption wavelength, excitation wavelength, and fluorescence wavelength of the Eu complex of the example (Eu complex represented by the above formula (1-4)) are shown in Figures 2 to 4. The measurement results of the absorption wavelength, excitation wavelength, and fluorescence wavelength of the Eu complex of the comparative example are shown in Figures 5 to 7.

[0090] <Preparation and Evaluation of Colored Resin Compositions> A resin solution was prepared by dissolving 2.0 g of general-purpose polystyrene resin and 0.050 g of the compound represented by formula (1-4) in 8.0 g of chloroform. The resin solution was applied to a glass plate using a bar coater, and the solvent was air-dried to create a colored resin film with a thickness of 10 μm. Absorption and fluorescence wavelength measurements were performed on this film. A Jasco V-650 spectrophotometer was used for absorption wavelength measurements. An Otsuka Electronics MCPD9800 was used for fluorescence wavelength measurements, with an excitation wavelength of 365 nm. The results of the absorption and fluorescence wavelength measurements are shown in Figures 8 and 9, respectively.

Claims

1. A resin composition comprising a rare earth complex and a resin, the rare earth complex includes one rare earth ion and a plurality of ligands coordinated to the rare earth ion; at least one of the plurality of ligands is a diketone ligand; at least one of the plurality of ligands is a phosphine oxide ligand having a chromophore that gives the rare earth complex a maximum absorption wavelength in a wavelength region of 400 to 600 nm; A resin composition, wherein the phosphine oxide ligand having a chromophore is a ligand represented by the following formula (III): 【Chemistry 1】 [In the formula, X １１ and X １２ are each independently an aromatic group, a heteroaromatic group, C １～１２ Alkyl group, C ３～１２ Alkenyl group, C ３～１２ Cycloalkyl group, C ３～１２ Cycloalkenyl group, C ３～１２ an alkynyl group, an aromatic oxy group (aromatic group -O-), a heteroaromatic oxy group (heteroaromatic group -O-), C １～１２ Alkyloxy group, C ３～１２ Alkenyloxy group, C ３～１２ Cycloalkyloxy group, C ３～１２ a cycloalkenyloxy group, or C ３～１２ represents an alkynyloxy group represented by the formula: Z １ represents a group represented by the following formula (Ib) or (IIa), in which * represents a bond to the phosphorus atom. 【Chemistry 2】 【Transformation 3】

2. The resin composition according to claim 1 , wherein the rare earth ions are Eu ions or Tb ions.

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