Rare earth organic complexes and their manufacturing methods and applications

Abstract

To provide a rare earth organic complex suitable for forming light conversion films, and a preparation method thereof.SOLUTION: The invention discloses a rare earth organic complex having a structure represented by formula (I) as well as a preparation method and application thereof. The anti-radiation performance of the rare earth organic complex is improved, and the rare earth organic complex has good absorption in an ultraviolet light area and a blue light area smaller than 500 nm, can be excited by light within the wavelength range of smaller than 460 nm, facilitates conversion into visible light at or larger than 500 nm and is suitable for preparing light conversion films.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a rare earth organic complex and its manufacturing method and application, and more particularly to a rare earth organic complex that can be used to form a light conversion film, and its manufacturing method and application. [Background technology]

[0002] Rare earth complexes have unique 4f emission characteristic peaks, making them ideal for producing light conversion materials. In photoluminescence, the ligands absorb energy from the excitation light source and transfer it to the core metal ion. The ligands play a very important role in improving the efficiency of light energy utilization.

[0003] A photoconversion film is a film in which a base material with photoconversion functionality is added to the raw materials used to manufacture ordinary films. The conversion agent contained in the photoconversion film can convert the high-energy short-wavelength light in sunlight into low-energy long-wavelength light and mid-long-wavelength light, or can increase the temperature of the cultivation rack to provide appropriate light irradiation conditions for crops, thereby promoting crop growth and increasing productivity.

[0004] Patent Document 1 discloses a biomimetic phosphor conversion agent for agricultural films, containing a diketone ligand, an aromatic carboxylic acid ligand, and a phosphonooxide-containing compound. The resulting phosphor conversion agent absorbs short-wavelength ultraviolet light in the 240-400 nm wavelength range and emits high-intensity blue light in the 400-500 nm wavelength range. Patent Document 2 discloses a rare earth organic complex conversion agent and its manufacturing method, which uses a diketone as a ligand and co-ligands such as o-phenanthroline, bipyridine, tri-n-octylphosphine oxide, and triphenylphosphine oxide. Patent Document 3 discloses a rare earth organic complex light conversion film prepared from a light conversion agent and auxiliary agent manufactured from raw materials including a substrate, rare earth oxide, diketone, and phenanthroline. Patent Document 4 discloses a method for producing a composite rare earth light conversion agent for agricultural films, which involves generating amino- and carboxyl-functionalized carbon moieties through a hydrothermal reaction of silk, and then using the polyamino and carboxyl groups on the surface to chelate rare earth ions and form multiple luminescent centers. Methylbenzodiazole is used as the primary ligand, o-phenanthroline as the co-ligand, and a surfactant is added. The resulting light conversion agent can convert the ultraviolet portion of sunlight into red-blue light, which is highly adaptable to photosynthesis in agricultural crops.

[0005] However, the poor UV resistance of the complexes limits their practical use. This is a fatal flaw in luminescent materials that must be resolved. To address this flaw, attempts to develop new ligands to obtain new rare earth organic complexes remain an important approach to the development of rare earth complex luminescent materials. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 1408810 [Patent Document 2] Chinese Patent Application Publication No. 101358128 [Patent Document 3] Chinese Patent Application Publication No. 101857690 [Patent Document 4] Chinese Patent Application Publication No. 108192598 Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the above, one object of the present invention is to provide a rare earth organic complex with improved radiation resistance. Furthermore, it has good absorption in the ultraviolet light region and the blue light region below 500 nm, and can be excited by light in the wavelength range below 460 nm and converted into visible light above 500 nm. This can be applied to the formation of a light conversion film. Another object of the present invention is to provide a method for producing the rare earth organic complex. Yet another object of the present invention is to provide applications of the rare earth organic complex. The present invention achieves the above objects by the following technical means.

[0008] In one aspect, the present invention provides a rare earth organic complex having a structure represented by formula (I):

[0009] [ka]

[0010] [In formula (I), Ln represents a trivalent rare earth metal ion, R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group; R8, R9, and R 10 are each independently selected from hydrogen and a C1-C4 alkyl group; R 11 are independently selected from hydrogen and C1 to C3 alkyl groups.

[0011] According to the rare earth organic complex of the present invention, preferably, R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; and R8, R9, and R 10 are each independently selected from hydrogen and a C1-C3 alkyl group; R 11are independently selected from hydrogen, a methyl group, or an ethyl group.

[0012] According to the rare earth organic complex of the present invention, preferably, R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen and a C1-C3 alkyl group; and R8, R9, and R 10 are each independently selected from hydrogen, a methyl group, or an ethyl group; R 11 are independently selected from hydrogen.

[0013] According to the rare earth organic complex of the present invention, preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently selected from hydrogen or a methyl group.

[0014] According to the rare earth organic complex of the present invention, Ln is preferably Eu 3+ , Sm 3+ , Tb 3+ , Dy 3+ The compound is one or more selected from the group consisting of:

[0015] The rare earth organic complex according to the present invention preferably has a structure represented by formula (II).

[0016] [ka]

[0017] In another aspect, the method includes the steps of: (1) stirring and mixing a water-soluble rare earth salt, a compound represented by formula (A), a compound represented by formula (B), and an alcohol solvent at 45 to 70°C to obtain an alcohol solution; (2) adding an alkali metal hydroxide solution to an alcohol solution to cause a reaction, lowering the temperature, allowing the mixture to stand, and performing solid-liquid separation to obtain a rare earth organic complex having a structure represented by formula (I).

[0018] [ka]

[0019] [In formula (A), R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group; In formula (B), R8, R9, R 10 are each independently selected from hydrogen and a C1-C4 alkyl group; R 11 are independently selected from hydrogen and C1-C3 alkyl groups; Here, the rare earth metal ion in the water-soluble rare earth salt is represented by Ln, and Ln is a trivalent rare earth metal ion, wherein the molar ratio of the compound represented by formula (A) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 1 to 1.05:1, and the molar ratio of the compound represented by formula (B) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 3 to 3.05:1; wherein the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, and n-butanol.

[0020] According to the method for producing a rare earth organic complex of the present invention, the alkali metal hydroxide is preferably selected from sodium hydroxide and / or potassium hydroxide.

[0021] According to the method for producing a rare earth organic complex of the present invention, the compound represented by formula (A) is preferably obtained by reacting a compound represented by formula (C) with a compound represented by formula (D).

[0022] [ka]

[0023] [wherein R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, a C1 to C6 alkyl group, or a C1 to C6 alkoxy group.]

[0024] In a further aspect, the present invention provides a method for producing a light conversion film, comprising: (1) mixing the rare earth organic complex with base particles for forming a polymer film, and pressing the mixture to obtain a light conversion film; (2) Use of a rare earth organic complex in the manufacture of a light conversion film, the method comprising the steps of: applying the rare earth organic complex to the surface of a polymer film to form a light rotation film; [Effects of the Invention]

[0025] The rare earth organic complex of the present invention has improved radiation resistance and can extend the service life of the complex. This rare earth organic complex has good absorption in the ultraviolet light region and the blue light region below 500 nm, and can be excited by light in the wavelength range below 460 nm and converted into visible light above 500 nm. This rare earth organic complex can be used in a light conversion film, and can effectively convert ultraviolet light and blue light into visible light above 500 nm. [Brief explanation of the drawings]

[0026] [Figure 1] 1 is an X-ray diffraction single crystal structure of the rare earth organic complex Eu(TTA)3BIP obtained in Example 1 of the present invention. [Figure 2] 1 is a fluorescence excitation spectrum of the rare earth organic complex Eu(TTA)3BIP obtained in Example 1 of the present invention. [Figure 3] 1 is a fluorescence emission spectrum of the rare earth organic complex Eu(TTA)3BIP obtained in Example 1 of the present invention. [Figure 4] FIG. 1 is a comparative diagram of the radiation resistance of the rare earth organic complex Eu(TTA)3BIP obtained in Example 1 of the present invention. [Figure 5] FIG. 2 is a transmittance diagram of the light conversion film manufactured in Use Example 1 of the present invention. [Figure 6] This is a comparison diagram of the light conversion effects of the light conversion film of Example 1 of the present invention and a simple polyethylene film. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will be further described below with reference to specific examples, which should not be construed as limiting the scope of the present invention.

[0028] <Terminology> In the present invention, Cm-Cn indicates that the group has m to n carbon atoms, for example, a C1-C6 alkyl group represents an alkyl group having 1 to 6 carbon atoms.

[0029] As used herein, "alkyl" refers to a group derived from a straight or branched chain aliphatic hydrocarbon having one point of attachment.

[0030] <Rare earth organic complexes>

[0031] The rare organic complex of the present invention has a structure represented by formula (I).

[0032] [ka]

[0033] Such rare earth organic complexes can be used as light conversion agents in the formation of light conversion films, which can effectively convert blue light and ultraviolet light with wavelengths of 500 nm or less into visible light with other wavelengths, thereby improving their radiation resistance.

[0034] In formula (I), Ln represents a trivalent rare earth metal ion. Preferably, Ln is Eu 3+ , Sm 3+ , Tb 3+ , Dy 3+ More preferably, Ln is Eu 3+ , Sm 3+ , Tb 3+ , Dy 3+ It is one selected from the above.

[0035] R1 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0036] R2 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0037] R3 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0038] R4 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0039] R5 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0040] R6 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0041] R7 can be selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group, preferably hydrogen or a C1-C6 alkyl group, more preferably hydrogen or a C1-C3 alkyl group, and even more preferably hydrogen, a methyl group, or an ethyl group.

[0042] In the present invention, examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and hexyl groups. Examples of C1-C6 alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy groups.

[0043] According to a specific embodiment of the present invention, R1, R2, R3, R4, R5, R6, R7 are all hydrogen.

[0044] R8 can be selected from hydrogen and C1-C4 alkyl, preferably hydrogen and C1-C3 alkyl, more preferably hydrogen, methyl or ethyl. In the present invention, examples of the C1-C4 alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, and a butyl group.

[0045] R9 can be selected from hydrogen, C1-C4 alkyl, preferably hydrogen, C1-C3 alkyl, more preferably hydrogen, methyl or ethyl.

[0046] R 10 can be selected from hydrogen, C1-C4 alkyl, preferably selected from hydrogen, C1-C3 alkyl, more preferably selected from hydrogen, methyl or ethyl.

[0047] According to one specific embodiment of the present invention, R8, R9, R 10 are all hydrogen.

[0048] R 11 are independently selected from hydrogen, a C1-C3 alkyl group, preferably hydrogen, a methyl group, or an ethyl group, more preferably hydrogen or a methyl group. 11 is hydrogen.

[0049] According to one embodiment of the present invention, the rare earth organic complex has a structure represented by formula (II):

[0050] [ka]

[0051] [In formula (II), Ln represents a trivalent rare earth metal ion.]

[0052] <Method of producing rare earth organic complex>

[0053] The method for preparing a rare earth organic complex of the present invention includes a step of mixing and dissolving raw materials, a step of forming a rare earth organic complex, and optionally a step of forming a 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand, as described in detail below.

[0054] Formation step of 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand

[0055] The compound of formula (C) is reacted with the compound of formula (D) to obtain the compound of formula (A), 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand.

[0056] [ka]

[0057] The substituents R1 to R7 in formula (C) and formula (D) are as described above and will not be described in detail here.

[0058] The molar ratio of the compound represented by formula (C) to the compound represented by formula (D) is 1:1.05 to 1.25, preferably 1:1.1 to 1.25, and more preferably 1:1.15 to 1.2.

[0059] The reaction temperature is 155 to 170° C., preferably 160 to 170° C., and more preferably 160 to 165° C. The reaction time is 1.5 to 4 hours, preferably 2 to 4 hours, and more preferably 2 to 3 hours.

[0060] In the present invention, 2-cyanopyrimidine and p-phenylenediamine can be directly mixed under an inert gas atmosphere, without the need for a solvent. The inert gas may be argon or nitrogen. After mixing, the two are directly heated and reacted. After the reaction is complete, the reaction product is dissolved in ethanol, filtered, insoluble matter is removed by filtration, the pressure is reduced, and the solvent is evaporated to obtain a compound represented by formula (A).

[0061] In formula (I), the 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand is the primary ligand, and the β-diketone-based ligand is the secondary ligand.

[0062] Raw material mixing and melting step

[0063] A water-soluble rare earth salt, a compound represented by formula (A) and a compound represented by formula (B) are mixed with an alcohol solvent to obtain an alcohol solution.

[0064] In one embodiment, the compound represented by formula (A) and the compound represented by formula (B) are mixed with an alcohol solvent, and then a water-soluble rare earth salt is added thereto and mixed to obtain an alcohol solution.

[0065] [ka]

[0066] R8 to R in formula (B) 11 The limitations of the substituents are as described above and will not be described in detail here.

[0067] The rare earth ions in water-soluble rare earth salts are denoted as Ln, where Ln is a trivalent rare earth metal ion, and Ln is Eu 3+ , Sm 3+ , Tb 3+ , Dy 3+ More preferably, Ln is Eu 3+ , Sm 3+ , Tb 3+ , Dy 3+ Ln is one selected from the group consisting of Eu 3+ , Sm 3+ , Tb 3+ , or Dy 3+ The water-soluble rare earth salt may be a rare earth nitrate, a chlorinated rare earth, or a rare earth sulfate, and is preferably a chlorinated rare earth. The water-soluble rare earth salt may be a rare earth salt having water of crystallization or a rare earth salt not having water of crystallization.

[0068] The molar ratio of the compound represented by formula (A) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 1 to 1.05:1, preferably 1 to 1.03:1, and more preferably 1.01 to 1.02:1. The molar ratio of the compound represented by formula (B) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 3 to 3.05:1, preferably 3 to 3.03:1, and more preferably 3.01 to 3.02:1.

[0069] The alcohol solvent is one or more selected from methanol, ethanol, isopropanol or n-butanol, preferably one selected from methanol, ethanol, isopropanol or n-butanol, more preferably methanol or ethanol.

[0070] The mixture may be heated during mixing, and the heating temperature is 45 to 70°C, preferably 55 to 70°C, and more preferably 60 to 65°C.

[0071] Rare earth organic complex formation step

[0072] The alkali metal hydroxide solution is added to the alcohol solution to cause a reaction, the temperature is lowered, the mixture is allowed to stand, and solid-liquid separation is carried out to obtain a rare earth organic complex having a structure represented by formula (I).

[0073] The alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide, preferably sodium hydroxide. The concentration of the alkali metal hydroxide solution may be 0.5 to 5 mol / L, preferably 1 to 4 mol / L, more preferably 1 to 3 mol / L.

[0074] In some embodiments, an alkali metal hydroxide solution is added dropwise to an alcohol solution at 55 to 70°C to react until no more precipitates are formed, and then the temperature is lowered to room temperature, the mixture is allowed to stand for 5 to 12 hours, and solid-liquid separation is performed to obtain crystals, i.e., a rare earth organic complex having a structure represented by formula (I) is obtained.

[0075] In formula (I), the coordination number of Ln is 8, providing two coordination sites for the 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand and two coordination sites for each of the three β-diketone-based ligands. The present inventors have discovered that 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole has significant advantages as a neutral ligand and can enhance the UV resistance of rare earth organic complexes.

[0076] <Use>

[0077] The present invention further provides a use of the rare earth organic complex as described above in the production of a light conversion film. Specifically, the rare earth organic complex is used as a light conversion agent in the production of a light conversion film.

[0078] For use, the rare earth organic complex can be coated on the surface of a polymer film to form a light conversion film. The coating method can be one known in the art. Alternatively, the rare earth organic complex can be mixed with the base particles forming the polymer film and pressed to obtain a light conversion film. The pressing method can be one known in the art, and will not be described in detail here.

[0079] The polymer film may be one of polyethylene terephthalate (PET), polyethylene (PE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE) or ethylene-tetrafluoroethylene copolymer (ETFE), preferably polyethylene.

[0080] The mass ratio of the rare earth organic complex to the base particles forming the polymer film can be 0.01 to 0.15:10, preferably 0.05 to 0.1:10.

[0081] In the present invention, the light conversion film formed can have a lower transmittance of blue light below 500 nm, and can effectively absorb blue light and ultraviolet light and convert them into red light.

[0082] <Test Method>

[0083] Fluorescence excitation and emission spectra were examined by a Horiba FL-3 spectrofluorometer. 1 H NMR spectra were run on a Bruker Avance III HD 500 MHz nuclear magnetic resonance spectrometer. Single crystal data were collected using a Bruker SMART APEX II X-ray diffractometer.

[0084] <Raw material source>

[0085] In the following examples, EuCl3·6H2O (99.9%), SmCl3·6H2O (99.9%), TbCl3·6H2O (99.9%), and DyCl3·6H2O (99.9%) were purchased from Shanghai Aladdin Reagents Co., Ltd. 2-Cyanopyrimidine (98%), p-phenylenediamine (98%), and 2-thenoyltrifluoroacetone (TTA, 98%) were purchased from Macklin Biochemical Technology Co., Ltd. Example 1

[0086] Reaction equation: [ka]

[0087] In a N2 atmosphere, 1.05 g (0.010 mol) of 2-cyanopyrimidine and 1.30 g (0.012 mol) of p-phenylenediamine were mixed and heated to 160°C with stirring. As the temperature increased, the solid dissolved into a liquid. As the reaction progressed to completion, a new compound was formed and the reaction mixture converted to a solid. This process took approximately 2 hours. The product was dissolved in ethanol, and the insoluble material was filtered. The solvent was evaporated under reduced pressure to give 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole.

[0088] The structural characteristics of 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole are: 1 H NMR (CDCl3, 500 Hz): δ 10.45 (1H), 8.90 (2H), 7.60 (1H), 7.36 (2H), 6.75 (2H).

[0089] At 60 °C, EuCl3·6H2O (99.9%) (0.37 g, 1 mmol) was added to an ethanolic solution of 50 mL of 2-thiopheneformyltrifluoroacetone (0.67 g, 3 mmol) and 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole (0.20 g, 1 mmol) to obtain an alcoholic solution. 1 M NaOH solution was added dropwise to the alcoholic solution, and the reaction mixture was controlled until no precipitate remained. The solution was cooled, allowed to stand overnight, and filtered to obtain the rare earth europium organic complex Eu(TTA)3BIP.

[0090] The rare earth europium organic complex Eu(TTA)3BIP of this example was characterized.

[0091] The single crystal structure test results are shown in Figure 1. The fluorescence excitation and emission spectrum test results are shown in Figures 2 and 3, respectively. Figure 4 shows the comparison of the radiation resistance properties of the rare earth europium organic complex Eu(TTA)3BIP and the β-diketone ligand Eu complex Eu(TTA)3.

[0092] As can be seen from the figure, the rare earth europium organic complex Eu(TTA)3BIP has good absorption in the ultraviolet region and the blue light region below 500 nm, and is excited by light in the wavelength range below 500 nm, with the optimal excitation wavelength being 394 nm. The main peaks in the fluorescence emission spectrum are at 594, 612, 653, and 701 nm, which indicates that trivalent Eu 3+ Aeon 5 D0→ 7 F1, 5 D0→ 7 F2, 5 D0→ 7 This was attributed to the characteristic emission of F3 and 5D0 → 7F4, manifested as a bright red light. After 180 minutes of irradiation, the fluorescence emission intensity of the rare earth europium organic complex Eu(TTA)3BIP only lost about 10%, while that of the complex Eu(TTA)3 lost nearly 80%, demonstrating the significant improvement in the radiation resistance stability of the rare earth europium organic complex Eu(TTA)3BIP of the present invention. The present invention suggests that the introduction of the 2-(pyrimidin-2-yl)-1H-benzo[d]imidazole ligand can enhance the radiation stability of the complex. Examples 2 to 4

[0093] The difference from Example 1 is that the water-soluble rare earth salts used in Examples 2 to 4 were TbCl3·6H2O (99.9%), SmCl3·6H2O (99.9%), and DyCl3·6H2O (99.9%), respectively, and rare earth organic complexes were obtained, the structures of which are shown in formula (102), formula (103), and formula (104).

[0094] [ka]

[0095] Usage example 1 The rare earth organic complex Eu(TTA)3BIP prepared in Example 1 was ground in an agate mortar to obtain a fine, homogenous complex powder. Next, 0.1 g of the Eu(TTA)3BIP complex and 10 g of linear low-density polyethylene base particles were weighed and prepared. The 0.1 g of Eu(TTA)3BIP complex and 10 g of linear low-density polyethylene base particles were uniformly mixed in a twin-screw kneader at 120°C to obtain a mixed base material. The mixed base material was then pressed into a light conversion film at 120°C using a platen vulcanizer.

[0096] The transmittance test results for the pressed light conversion film are shown in Figure 5. In Figure 5, polyethylene film refers to a simple film without the addition of rare earth organic complexes, and Eu(TTA)3BIP polyethylene film refers to the light conversion film produced in Use Example 1. As can be seen from Figure 5, the light conversion film with the addition of rare earth organic complex Eu(TTA)3BIP has a lower blue light transmittance below 500 nm than the simple polyethylene film, and can effectively absorb ultraviolet and blue light and convert it to red light. Figure 6 is a physical diagram of the light conversion film obtained in Use Example 1.

[0097] The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions that may occur to those skilled in the art without departing from the essential content of the present invention are included within the scope of the present invention.

Claims

1. A rare earth organic complex having a structure represented by formula (I), 【Chemistry 1】 [In formula (I), Ln represents a trivalent rare earth metal ion, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ are each independently selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group; R ８ , R ９ , R １０ are each independently selected from hydrogen and a C1-C4 alkyl group; R １１ are independently selected from hydrogen and C1-C3 alkyl groups.

2. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ are each independently selected from hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R ８ , R ９ , R １０ are each independently selected from hydrogen and a C1-C3 alkyl group; R １１ 2. The rare earth organic complex of claim 1, wherein is independently selected from hydrogen, a methyl group, or an ethyl group.

3. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ are each independently selected from hydrogen and a C1-C3 alkyl group; R ８ , R ９ , R １０ are each independently selected from hydrogen, a methyl group, or an ethyl group; R １１ 2. The rare earth organic complex of claim 1, wherein:

4. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ 2. The rare earth organic complex according to claim 1, wherein each of is independently selected from hydrogen or a methyl group.

5. Ln is Eu ３＋ , Sm ３＋ , Tb ３＋ , Dy ３＋ 2. The rare earth organic complex according to claim 1, wherein the rare earth organic complex is one selected from the group consisting of:

6. The rare earth organic complex according to claim 1, characterized in that it has a structure represented by formula (II): 【Chemistry 2】 。

7. A method for producing the rare earth organic complex according to any one of claims 1 to 6, comprising the steps of: (1) mixing a water-soluble rare earth salt, a compound represented by formula (A), a compound represented by formula (B), and an alcohol solvent with stirring at 45 to 70°C to obtain an alcohol solution; (2) a method for producing a rare earth organic complex, the method comprising the steps of adding an alkali metal hydroxide solution to an alcohol solution to cause a reaction, lowering the temperature, allowing the mixture to stand, and performing solid-liquid separation to obtain a rare earth organic complex having a structure represented by formula (I); 【Transformation 3】 [In formula (A), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ are each independently selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group; In formula (B), R ８ , R ９ , R １０ are each independently selected from hydrogen and a C1-C4 alkyl group; R １１ are independently selected from hydrogen and a C1-C3 alkyl group; Here, the rare earth metal ion in the water-soluble rare earth salt is represented by Ln, and Ln is a trivalent rare earth metal ion, wherein the molar ratio of the compound represented by formula (A) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 1 to 1.05:1, and the molar ratio of the compound represented by formula (B) to the trivalent rare earth metal ion in the water-soluble rare earth salt is 3 to 3.05:1; wherein the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, and n-butanol.

8. 8. The method according to claim 7, wherein the alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide.

9. The method according to claim 7, wherein the compound represented by formula (A) is obtained by reacting a compound represented by formula (C) with a compound represented by formula (D). 【Chemistry 4】 [where R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ are each independently selected from hydrogen, a C1 to C6 alkyl group, or a C1 to C6 alkoxy group.

10. Use of the rare earth organic complex according to any one of claims 1 to 6 in the manufacture of a light conversion film, (1) mixing the rare earth organic complex with the base particles forming a polymer film and pressing to obtain a light conversion film; (2) Use of a rare earth organic complex in the manufacture of a light conversion film, characterized by including any one of the steps of: applying the rare earth organic complex to the surface of a polymer film to form a light conversion film.

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