An organic-inorganic hybrid light conversion agent, its preparation method and a light conversion adhesive film

Abstract

The present invention belongs to the field of photovoltaic materials. The present invention relates to an organic-inorganic hybrid light conversion agent, a preparation method thereof and a light conversion film. The preparation method of the organic-inorganic hybrid light conversion agent comprises the following steps: carrying out a substitution reaction on benzotriazole and liquid bromine to obtain an intermediate product I; carrying out a substitution reaction on the intermediate product I and a bromoester to obtain an intermediate product II; carrying out a coupling reaction on the intermediate product II and 4-(aniline)phenylboronic acid to obtain an intermediate product III; carrying out a substitution reaction on the intermediate product III and 2,4,6-trichloro-1,3,5-triazine to obtain an intermediate product IV; carrying out a substitution reaction on the intermediate product IV and an aminobenzoic acid derivative to obtain an intermediate product V; carrying out surface modification on the intermediate product V and photosensitive metal oxide whiskers to obtain the organic-inorganic hybrid light conversion agent. The present invention effectively solves the problems existing in the commonly used organic light conversion agent benzotriazole in the current encapsulation film, such as narrow and single absorption peak, low light utilization rate, poor stability and easy precipitation.

Description

Technical Field

[0001] The present invention relates to an organic-inorganic hybrid light conversion agent, a preparation method thereof, and a light conversion film. The present invention belongs to the field of photovoltaic materials. Background Art

[0002] EVA (ethylene-vinyl acetate copolymer) is a thermoplastic polymer material. As a packaging material for solar cells, it has many advantages, including low cost, easy molding, outstanding optical properties, excellent mechanical properties and electrical properties, etc. However, when used in harsh outdoor climate environments for a long time, EVA will age and turn yellow, resulting in a decrease in the photoelectric conversion efficiency of the battery module or failure due to short circuit damage. Ultraviolet aging is precisely the main factor causing the yellowing of the EVA film. The current technology is to add ultraviolet absorbers to EVA to reduce the damage of ultraviolet rays to the EVA film. The addition of ultraviolet absorbers converts ultraviolet light into low-energy heat energy, which cannot be utilized by solar cells, resulting in loss of light energy and reduction of the efficiency of solar cells.

[0003] Therefore, developing a packaging material, namely a light conversion film, that can completely absorb ultraviolet light in the sun and convert it into visible light that can be utilized by the battery module can not only effectively prevent the damage of ultraviolet rays to the battery module, but also have a gain effect on the photoelectric conversion efficiency of the battery.

[0004] The key to developing a packaging light conversion film lies in developing an efficient and stable light conversion agent. According to the literature, inorganic light conversion agents have advantages in stability, but there are compatibility problems with the matrix, which affects the light conversion efficiency; while organic light conversion agents have more advantages in terms of price, structure, and compatibility with the film; but there are problems with poor stability. Despite the above problems, currently, more research is still focused on organic light conversion agents. As one of the typical ones, the organic light conversion agent based on benzotriazole has only one absorption peak, approximately around 350 nm, and the effective absorption range is relatively narrow, and the absorption of ultraviolet light below 400 nm is not sufficient. This will cause the corresponding light conversion film to be unable to effectively absorb ultraviolet rays in sunlight, thus unable to effectively protect the battery module; the problem of poor stability has not been solved yet.

[0005] In view of the advantages and disadvantages of organic light conversion agents and inorganic light conversion agents, it is necessary to design a new type of light conversion agent that combines the compatibility of organic light conversion agents and the stability of inorganic light conversion agents to solve the technical problems existing in the current industry. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing an organic-inorganic hybrid light conversion agent for photovoltaics, in view of the problem that the light conversion agent used in the encapsulated light conversion adhesive film in the prior art cannot have both compatibility with the substrate and stability. The present invention prepares an organic-inorganic hybrid light conversion agent by molecular design, and effectively solves the above problems through formula design, and has broad application potential. The technical solution adopted by the present invention to solve its technical problems is:

[0007] A method for preparing an organic-inorganic hybrid light conversion agent comprises the following steps:

[0008] S11, subjecting benzotriazole to a substitution reaction with liquid bromine to obtain an intermediate product I;

[0009] S12, subjecting the intermediate product I to a substitution reaction with a bromoester to obtain an intermediate product II;

[0010] S13, coupling the intermediate product II with 4-(aniline)phenylboronic acid to obtain an intermediate product III;

[0011] S14, subjecting the intermediate product III to a substitution reaction with 2,4,6-trichloro-1,3,5-triazine to obtain an intermediate product IV;

[0012] S15, subjecting the intermediate product IV to a substitution reaction with an aminobenzoic acid derivative to obtain an intermediate product V;

[0013] S16, surface modification of the intermediate product V and photosensitive metal oxide whiskers to obtain an organic-inorganic hybrid light conversion agent.

[0014] Furthermore, the molar ratio of the benzotriazole to the liquid bromine is 1:(1.2-1.5).

[0015] Furthermore, the molar ratio of the intermediate product I to the bromoester is 1:(1.2-1.5).

[0016] Furthermore, the molar ratio of the intermediate product II to the 4-(aniline)phenylboronic acid is 1:(1.2-1.6).

[0017] Furthermore, the molar ratio of the intermediate product III to the 2,4,6-trichloro-1,3,5-triazine is (2.0-2.2):1.

[0018] Furthermore, the molar ratio of the intermediate product IV to the aminobenzoic acid derivative is 1:(1.0-1.2); the aminobenzoic acid derivative has 1 amino functional group and 1-3 carboxyl functional groups.

[0019] Further, the mass ratio of the intermediate product V to the photosensitive metal oxide whiskers is (0.5 - 2.0):10; the photosensitive metal oxide whiskers are selected from at least one of zinc oxide, titanium oxide, and copper oxide.

[0020] Another object of the present invention is to provide an organic-inorganic hybrid light conversion agent prepared by the preparation method as described above.

[0021] Another object of the present invention is to provide a light conversion adhesive film comprising the organic-inorganic hybrid light conversion agent as described above.

[0022] Further, it comprises raw materials in the following parts by weight:

[0023] 100 parts of polyolefin resin;

[0024] 0.5 - 1.5 parts of crosslinking agent;

[0025] 1.0 - 3.0 parts of co-crosslinking agent;

[0026] 2.0 - 10.0 parts of the organic-inorganic hybrid light conversion agent;

[0027] 0.05 - 0.25 parts of antioxidant;

[0028] 0.05 - 0.3 parts of light stabilizer;

[0029] 0.3 - 0.8 parts of coupling agent.

[0030] Further, the polyolefin resin is selected from at least one of EVA resin and POE resin.

[0031] Advantages of the present invention:

[0032] (1) The present invention provides an organic-inorganic hybrid light conversion agent for photovoltaic applications, which is a structure in which triazine-modified benzotriazole (organic structure) modifies the surface of photosensitive metal oxide (inorganic structure). Among them, the modified benzotriazole structure contains a large number of chemical structures such as benzene rings, triazine rings, and long fatty chain ester groups. First, through molecular structure design of benzotriazole, phenyl substitution can change its symmetry, resulting in a relatively wide ultraviolet absorption at 300-400 nm. At the same time, triazine has a large absorption in the ultraviolet region of 200-330 nm. Therefore, the triazine-modified benzotriazole structure can have a relatively wide absorption in the range of 250-400 nm. Second, in the organic-inorganic hybrid light conversion agent, benzotriazole, triazine, and photosensitive metal oxide excite carriers after absorbing ultraviolet light, and transfer energy through the conjugated structure and the photo-generated hole recombination effect of the photosensitive metal oxide. At the same time, the whisker structure of the photosensitive metal oxide has a larger specific surface area, which can effectively connect each organic light conversion structure to form a large conductive structure unit, thus greatly improving the light conversion efficiency. Third, the benzotriazole and triazine structures are both rigid structures, which can reduce the energy loss caused by the vibration of the molecular structure during the molecular luminescence process, further improving the light conversion efficiency. Fourth, the whisker structure of the photosensitive metal oxide has a special spatial structure, and the needle-like structure of the whisker can effectively increase the contact probability between each conductive structure unit to form a conductive network, further enhancing the light conversion efficiency. Fifth, the whisker structure in the whisker structure of the photosensitive metal oxide gives the light conversion agent a better anchoring effect and low migration property. Sixth, after triazine-modified benzotriazole modifies the photosensitive metal oxide, it gives the light conversion agent better system compatibility, and the long fatty chain ester group structure in the organic structure is beneficial to its dispersibility in the polyolefin matrix, synergistically improving the physical properties, etc. Finally, the organic-inorganic hybrid light conversion agent combines the advantages of good stability of inorganic light conversion agents and good dispersibility of organic light conversion agents.

[0033] (2) The present invention provides a light conversion film. The organic-inorganic hybrid light conversion agent in the formulation system converts the ultraviolet light that was originally absorbed by the ultraviolet light absorber and lost into visible light, making full use of the light, improving the photoelectric conversion efficiency of the solar cell, and at the same time avoiding the damage of ultraviolet light to the substrate film, which has great practical significance.

[0034] (3) The present invention provides a preparation method of an organic-inorganic hybrid light conversion agent. The preparation of the light conversion agent in the formulation system all uses common raw materials, and the light conversion film has an auxiliary light stabilizer effect after formulation design, which is highly operable for the industrialization of the products of the present invention. Description of the Drawings

[0035] The present invention will be further described below in conjunction with the drawings and embodiments.

[0036] Figure 1 is the 1H NMR spectrum of intermediate I in Example 1 of the present invention;

[0037] Figure 2 is the 1H NMR spectrum of intermediate II in Example 1 of the present invention;

[0038] Figure 3 is the 1H NMR spectrum of intermediate III in Example 1 of the present invention;

[0039] Figure 4 is the 1H NMR spectrum of intermediate IV in Example 1 of the present invention;

[0040] Figure 5 is the 1H NMR spectrum of intermediate V in Example 1 of the present invention;

[0041] Figure 6 is the 1H NMR spectrum of the organic-inorganic hybrid light conversion agent in Example 1 of the present invention. Detailed implementation manners

[0042] The present invention will be described in detail below in conjunction with embodiments. It should be understood that the following embodiments are only illustrative examples of the implementation manners of the present invention, rather than limiting the scope of the present invention.

[0043] The object of the present invention is to develop an organic-inorganic hybrid light conversion agent and a light conversion film for photovoltaic applications to meet the application requirements of existing photovoltaic packaging materials. The implementation idea is as follows: self-prepare an organic-inorganic hybrid light conversion agent for photovoltaic applications, which has high stability and light conversion efficiency while ensuring its compatibility and dispersibility in polyolefins. Specifically: asymmetric modification is carried out with benzotriazole as the parent body, an electron-rich benzene ring, and triazine bonding modification; and surface modification is carried out on photosensitive metal oxide whiskers to form an organic-inorganic hybrid structure. The theoretical basis for implementation is as follows: benzotriazole first undergoes a substitution reaction with liquid bromine, then a substitution reaction with bromoester, then a coupling reaction with phenylboronic acid, then a substitution reaction with secondary amino group, then a substitution reaction with amino group, and finally a surface modification reaction of carboxyl group with metal oxide to prepare an organic-inorganic hybrid light conversion agent. The above-mentioned organic-inorganic hybrid light conversion agent, through molecular structure design, has a larger absorption peak, higher compatibility and stability with the matrix, and higher light conversion efficiency, etc., and does not migrate and precipitate. The implementation method of the present invention is as follows:

[0044] The present invention provides a preparation method of an organic-inorganic hybrid light conversion agent, comprising the following steps:

[0045] S11. Add benzotriazole to hydrobromic acid, stir, slowly dropwise add liquid bromine to the reaction system, heat under reflux for 18 - 24 h, then quench with saturated aqueous sodium bisulfite solution, extract with dichloromethane, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry under vacuum at 40 °C for 8 h to obtain intermediate I.

[0046] The dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated aqueous sodium bisulfite solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol : 0.75 mol : 0.12 - 0.15 mol : 400 mL : 300 mL : 5 g.

[0047] S12. Take intermediate I, potassium carbonate, and bromoester, add them to N,N - dimethylformamide, stir and heat at 40 - 60 °C for 40 - 48 h. After the reaction ends, cool to room temperature, wash 3 times with saturated ammonium chloride solution, extract with ethyl acetate, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry under vacuum at 40 °C for 8 h to obtain intermediate II.

[0048] The dosage ratio of intermediate I, potassium carbonate, bromoester, N,N - dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol : 0.25 mol : 0.12 - 0.15 mol : 200 mL : 300 mL : 400 mL : 5 g.

[0049] The number of carbon atoms of the bromoester is C 6 -C 10 , so as to avoid that when the number of C atoms > 10, the reaction activity is low, which affects the reaction efficiency and has an adverse effect on the subsequent reaction efficiency and product; when the number of C atoms < 6, the molecular chain is too small to form good compatibility with the matrix resin, affecting the product performance; therefore, in the present invention, the bromoester can be ethyl 4 - bromovalerate, ethyl 5 - bromovalerate, ethyl 6 - bromohexanoate, ethyl 7 - bromoheptanoate, tert - butyl 5 - bromovalerate, ethyl 8 - bromooctanoate, etc.; and preferably, tert - butyl 5 - bromovalerate.

[0050] S13. Take intermediate II, 4 - (phenylamino)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium, mix them and add them to a reactor, N 2 Replace and protect; after adding the mixed solvent, stir and heat under reflux for 12 - 24 h, then add deionized water and shake, extract with dichloromethane, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry under vacuum at 40 °C for 8 h to obtain intermediate III.

[0051] The dosage ratio of intermediate II, 4-(phenylamino)phenylboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.12 - 0.16 mol: 0.5 mol: 0.005 - 0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0052] The mixed solvent is a mixture of toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0053] In the coupling reaction of 4-(phenylamino)phenylboronic acid and intermediate II in the present invention, there may be substitution coupling reactions of the boronic acid group and the secondary amino group with the bromine in intermediate II respectively. However, the reaction activity of the boronic acid group is higher than that of the secondary amino group, and the coupling reaction of the secondary amino group usually requires an environment with a strong base. Therefore, under the same conditions, the boronic acid group preferentially undergoes a coupling reaction with the bromobenzene structure.

[0054] S14, the reaction system is purged with N 2 to displace the gas and protect it with nitrogen. Intermediate III is added to tetrahydrofuran A, stirred magnetically, n-butyllithium is added, and it is cooled in an ice bath. After stirring for 15 min, it is added dropwise to tetrahydrofuran B containing 2,4,6-trichloro-1,3,5-triazine using a peristaltic pump. After the addition is completed, it is heated under reflux for 5 - 8 h; then it is cooled to room temperature, deionized water is injected, and after stirring for 15 min, an insoluble substance is obtained. The insoluble substance is filtered, recrystallized with dichloromethane and n-hexane, and vacuum dried at 40 °C for 8 h to obtain intermediate IV.

[0055] The dosage ratio of intermediate III, tetrahydrofuran A, n-butyllithium, 2,4,6-trichloro-1,3,5-triazine, tetrahydrofuran B, and deionized water is 0.20 - 0.22 mol: 200 mL: 0.20 - 0.25 mol: 0.1 mol: 300 mL: 800 mL.

[0056] S15, intermediate IV and the aminobenzoic acid derivative are added to anhydrous tetrahydrofuran, heated under reflux for 10 - 20 h, and then the Ehrlich reagent is used to confirm the end point of the reaction; after the reaction is completed, a saturated sodium chloride solution is added, allowed to stand, an insoluble substance is produced, the insoluble substance is filtered, washed with deionized water, and vacuum dried at 40 °C for 8 h to obtain intermediate V.

[0057] The dosage ratio of intermediate IV, the aminobenzoic acid derivative, anhydrous tetrahydrofuran, saturated sodium chloride solution, and deionized water is 0.1 mol: 0.10 - 0.12 mol: 200 mL: 300 mL: 500 mL.

[0058] The amino functional group of the aminobenzoic acid derivative is 1, and the carboxyl functional group is 1 - 3;

[0059] The aminobenzoic acid derivatives with 1 carboxyl functional group can be p-aminobenzoic acid, m-aminobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-amino-4-methylbenzoic acid, etc.; and preferably p-aminobenzoic acid;

[0060] The aminobenzoic acid derivatives with 2 carboxyl functional groups can be 4-aminophthalic acid, 4-aminoisophthalic acid, etc.; and preferably 4-aminophthalic acid;

[0061] The aminobenzoic acid derivatives with 3 carboxyl functional groups can be 2-aminobenzene-1,3,5-tricarboxylic acid, 1-aminobenzene-3,4,5-tricarboxylic acid, etc.; and preferably 1-aminobenzene-3,4,5-tricarboxylic acid.

[0062] S16. Add the intermediate product V and the photosensitive metal oxide whiskers into anhydrous acetone, stir magnetically at 80 - 90 °C for 2 - 3 h, then pour the mixed solution into a petri dish and dry it under vacuum at 100 °C for 48 h to obtain the intermediate product V, that is, the organic-inorganic hybrid light conversion agent.

[0063] The dosage ratio of the intermediate product V, the photosensitive metal oxide whiskers, and anhydrous acetone is 0.5 - 2.0 g : 10 g : 200 mL.

[0064] The photosensitive metal oxide whiskers are zinc oxide, titanium oxide, or copper oxide;

[0065] In the present invention, preferably, the zinc oxide whiskers are tetrapod-like zinc oxide whiskers with a special three-dimensional structure; purchased from Chengdu Jiaoda Jingyu Technology Co., Ltd., brand AT-01, and the specification is 10 - 20 μm.

[0066] The preparation method of the preferred titanium oxide whiskers refers to the method described in the literature (Zhang Yanping, etc.; Preparation and oil-soluble properties of TiO 2 Preparation of nanowhiskers and their oil-soluble properties research [J]. Journal of Bohai University (Natural Science Edition), 2017, 38(2): 156 - 160)), and they are nanowire structures with a diameter of 60 - 100 nm and an aspect ratio of 25:1.

[0067] The preparation method of the copper oxide whiskers refers to the method described in the literature (Li Su, etc.; Preparation of copper oxide whiskers by electrochemical method [J]: 2010, 61: 112 - 115.), and they are one-dimensional structures with a diameter of 60 - 100 nm, a length of 0.5 - 1 μm, and an aspect ratio of 8 - 10.

[0068] In the present invention, the photosensitive metal oxide whisker structure can specifically be zinc oxide whisker, titanium oxide whisker, or copper oxide whisker. First, the light conversion efficiency of zinc oxide, titanium oxide, and copper oxide as the light conversion agent structure can all reach a relatively high level. Second, in terms of physical structure, the zinc oxide whisker can be a tetrapod-like zinc oxide whisker, which is a three-dimensional tetrapod-like shape with a regular three-dimensional spatial structure. Four needle-like crystals extend from the core in the radial direction, and each needle-like body is a single crystal microfiber with a nanoscale size. This can effectively increase the contact probability of each needle-like body and form a conductive path to the greatest extent. At the same time, the four-needle-like spatial structure enables it to be effectively and evenly dispersed in the matrix, and its comprehensive properties such as the anchoring effect are better. The titanium oxide whisker and copper oxide whisker are one-dimensional nanowire structures, with good light conversion and conductivity properties as well as low migration properties.

[0069] The preparation process of the organic-inorganic hybrid light conversion agent in the present invention is as follows. This preparation process is only for reference and illustration and does not limit the present invention:

[0070] 。

[0071] Another object of the present invention is to provide an organic-inorganic hybrid light conversion agent, which is prepared by the method described above.

[0072] The organic-inorganic hybrid light conversion agent in the present invention is an organic structure modifying an inorganic structure, specifically, triazine-modified benzotriazole modifying the photosensitive metal oxide whisker. By modifying the inorganic structure with the organic structure, the dispersibility of the inorganic structure in the matrix is effectively improved. Through molecular structure design, triazine, asymmetric benzotriazole, and long-chain ester groups are used to improve the compatibility with the matrix. In the light conversion agent, triazine, benzene ring, benzotriazole, etc. form a conjugated structure, effectively broadening the absorption peak width in the ultraviolet region, enhancing the electron transport ability, and improving the light conversion efficiency. At the same time, it anchors to the matrix with the whisker structure, increasing the contact probability of each light conversion structural unit and forming a conductive network with a "quasi-macromolecule" structure macroscopically, which can effectively improve properties such as luminous efficiency and photoelectric gain. In the organic-inorganic hybrid light conversion agent structure of the present invention, each chemical structure has a synergistic effect to promote and improve the light conversion efficiency.

[0073] The present invention also provides a light conversion film, the raw materials of which include the organic-inorganic hybrid light conversion agent described above. Specifically, preferably, the raw materials include the following parts by weight:

[0074] Polyolefin resin: 100 parts;

[0075] Crosslinking agent: 0.5 - 1.5 parts;

[0076] Co-crosslinking agent: 1.0 - 3.0 parts;

[0077] Organic-inorganic hybrid light conversion agent: 2.0 - 10.0 parts;

[0078] Antioxidant: 0.05 - 0.25 parts;

[0079] Light stabilizer: 0.05 - 0.3 parts;

[0080] Coupling agent: 0.3 - 0.8 parts.

[0081] Furthermore, the polyolefin resin is selected from at least one of EVA resin and POE resin.

[0082] Wherein, when the polyolefin resin is EVA resin, the light conversion film preferably comprises the following raw materials in parts by weight:

[0083] EVA resin: 100 parts;

[0084] Crosslinking agent: 0.5 - 1.5 parts;

[0085] Co-crosslinking agent: 1.0 - 3.0 parts;

[0086] Organic-inorganic hybrid light conversion agent: 2.0 - 10.0 parts;

[0087] Antioxidant: 0.1 - 0.25 parts;

[0088] Light stabilizer: 0.1 - 0.3 parts;

[0089] Coupling agent: 0.3 - 0.5 parts.

[0090] When the polyolefin resin is POE resin, the light conversion film preferably comprises the following raw materials in parts by weight:

[0091] POE resin: 100 parts;

[0092] Crosslinking agent: 0.5 - 1.5 parts;

[0093] Co-crosslinking agent: 1.0 - 3.0 parts;

[0094] Organic-inorganic hybrid light conversion agent: 2.0 - 10.0 parts;

[0095] Antioxidant: 0.05 - 0.20 parts;

[0096] Light stabilizer: 0.05 - 0.20 parts;

[0097] Coupling agent: 0.4 - 0.8 parts.

[0098] In the present invention, the EVA resin preferably has a VA content of 28-33%. Without special instructions, the EVA resin in the following examples and comparative examples of the present invention is preferably an EVA resin with a VA content of 33% and a melt index (MI) of 31 purchased from DuPont Company, USA.

[0099] Without special instructions, the POE resin in the following examples and comparative examples of the present invention has the model number XUS38660 and is purchased from Dow Chemical Company, USA.

[0100] The crosslinking agent in the present invention is an organic peroxide type, specifically it can be benzoyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, dicyclohexyl peroxydicarbonate or diisopropylbenzene peroxide, etc.; without special instructions, the crosslinking agent in the following examples and comparative examples of the present invention is benzoyl peroxide.

[0101] The co-crosslinking agent in the present invention is a polyfunctional allyl type and / or acryloyloxy type.

[0102] Among them, the allyl type co-crosslinking agent can be triallyl cyanurate or triallyl isocyanurate, etc.

[0103] The acryloyloxy type co-crosslinking agent can be any combination of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, pentaerythritol triacrylate.

[0104] Without special instructions, the co-crosslinking agent in the following examples and comparative examples of the present invention is added in a mass ratio of 10:2:4 of triallyl isocyanurate, trimethylolpropane trimethacrylate, and propoxylated trimethylolpropane triacrylate.

[0105] The antioxidant in the present invention is used by compounding a hindered phenol type and a phosphite type. The hindered phenol type antioxidant can be antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 2246, etc.; and preferably antioxidant 1010. The phosphite antioxidant can be antioxidant 168, antioxidant 242, antioxidant TPP, etc.; and preferably antioxidant 168. Without special instructions, the antioxidant in the following examples and comparative examples of the present invention is added in a mass ratio of 1:2 of antioxidant 1010 and antioxidant 168.

[0106] In the present invention, the light stabilizer is a hindered amine type light stabilizer to avoid competition with the light conversion agent for ultraviolet rays. The hindered amine type light stabilizer can be UV-292, UV-770 or GW540, etc.; and preferably UV-292. Without special instructions, the light stabilizer in the following examples and comparative examples of the present invention is UV-292.

[0107] In the following embodiments of the present invention, the coupling agent is a silane coupling agent, specifically a vinyl silane coupling agent, which may be KH151, KH171 or KH172, etc.; and preferably KH172.

[0108] To better understand the above invention, the present invention also provides a method for preparing a light conversion film. Unless otherwise specified, the following operations are carried out, including the following steps:

[0109] S21, mixing materials, that is

[0110] Put the raw materials in proportion into a mixer and mix and stir at a temperature of 40 °C and a rotation speed of 80 rpm for 2 h to obtain a mixed raw material;

[0111] S22, extrusion;

[0112] Specifically, the EVA extrusion process is as follows:

[0113] Put the mixed raw material in S21 into a twin-screw extruder and melt-blend and extrude at a temperature of 80 °C in zone 1, 90 °C in zone 2, 98 °C in zone 3, a die head temperature of 102 °C, and a rotation speed of 50 rpm. Extrude through a cast film die head and cast, and cool through a casting roll;

[0114] The POE extrusion process is as follows:

[0115] Put the mixed raw material in S21 into a twin-screw extruder and melt-blend and extrude at a temperature of 90 °C in zone 1, 100 °C in zone 2, 105 °C in zone 3, a die head temperature of 110 °C, and a rotation speed of 50 rpm. Extrude through a cast film die head and cast, and cool through a casting roll;

[0116] The EPE co-extrusion process is as follows:

[0117] Put the EVA layer raw material in S21 into a twin-screw extruder and melt-blend at a temperature of 80 °C in zone 1, 90 °C in zone 2, 98 °C in zone 3, a die head temperature of 102 °C, and a rotation speed of 50 rpm; put the POE raw material in S21 into a twin-screw extruder and melt-blend at a temperature of 90 °C in zone 1, 100 °C in zone 2, 105 °C in zone 3, a die head temperature of 110 °C, and a rotation speed of 50 rpm; Extrude through a co-extrusion cast film die head and cast, and cool through a casting roll;

[0118] S23, film forming, that is

[0119] After thickness measurement, edge pressing, shaping, and then edge trimming and winding, the light conversion film with a thickness of 500 μm is obtained;

[0120] Among them, for the EPE-encapsulated light conversion film, its total thickness is 500 μm.

[0121] To further understand the present invention, the organic-inorganic hybrid light conversion agent and light conversion film provided by the present invention will be described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0122] Example 1

[0123] A preparation method of an organic-inorganic hybrid light conversion agent includes the following steps:

[0124] S11: Add benzotriazole to hydrobromic acid, stir, slowly drop liquid bromine into the reaction system, and after heating under reflux for 20 h, add a saturated aqueous solution of sodium bisulfite to quench, extract with dichloromethane, separate the liquid, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40 °C for 8 h to obtain intermediate I;

[0125] The dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated aqueous solution of sodium bisulfite, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.14 mol: 400 mL: 300 mL: 5 g.

[0126] Its nuclear magnetic resonance hydrogen spectrum is shown in Figure 1 as follows, and the nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR(400MHz, CDCl 3 , δ ppm):7.2 - 7.8(3H, benzene ring); 10.22(1H, -NH-).

[0127] S12: Take intermediate I, potassium carbonate, tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 50 °C for 46 h, cool to room temperature after the reaction, wash 3 times with a saturated ammonium chloride solution, extract with ethyl acetate, separate the liquid, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and vacuum dry at 40 °C for 8 h to obtain intermediate II.

[0128] The dosage ratio of intermediate I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.14 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0129] Its nuclear magnetic resonance hydrogen spectrum is shown in Figure 2 as follows, and the nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR(400MHz, CDCl 3, δ ppm): 7.2 - 7.8 (3H, benzene ring); 3.32 (2H, -N-CH 2 -); 1.29 (4H, -CH 2 -); 2.31 (2H, -CH 2 -COO-); 1.20 (9H, -CH 3 ).

[0130] S13. The intermediate product II, 4-(phenylamino)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium were mixed and added to a reactor, and protected by N2 replacement. After adding the mixed solvent, it was stirred and heated under reflux for 20 h. Then deionized water was added and shaken, and extracted with dichloromethane. After liquid separation, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, and the solution was taken. It was separated by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dried at 40 °C for 8 h to obtain intermediate product III.

[0131] The usage ratios of the intermediate product II, 4-(phenylamino)phenylboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate were 0.1 mol: 0.14 mol: 0.5 mol: 0.008 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0132] The mixed solvent was a mixture of toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0133] Its 1H NMR spectrum is shown in Figure 3 as follows, and the 1H NMR data are as follows: 1 H NMR (400 MHz, CDCl 3 , δ ppm): 7.2 - 7.8 (12H, benzene ring); 5.63 (1H, -NH-); 3.32 (2H, -N-CH 2 -); 1.29 (4H, -CH 2 -); 2.31 (2H, -CH 2 -COO-); 1.20 (9H, -CH 3 ).

[0134] S14. The reaction system was purged with N 2 and protected with nitrogen. The intermediate product III was added to tetrahydrofuran A, and stirred magnetically. Then n-butyllithium was added, and it was cooled in an ice bath. After stirring for 15 min, it was added dropwise to tetrahydrofuran B containing 2,4,6-trichloro-1,3,5-triazine by a peristaltic pump. After the addition was completed, it was heated under reflux for 6 h. Then it was cooled to room temperature, deionized water was injected, and stirred for 15 min to obtain an insoluble substance. The insoluble substance was filtered, recrystallized with dichloromethane and n-hexane, and vacuum dried at 40 °C for 8 h to obtain intermediate product IV.

[0135] The dosage ratio of intermediate III, tetrahydrofuran A, n-butyllithium, 2,4,6-trichloro-1,3,5-triazine, tetrahydrofuran B, and deionized water is 0.22 mol: 200 mL: 0.22 mol: 0.1 mol: 300 mL: 800 mL.

[0136] Its 1H NMR spectrum is shown in Figure 4 as follows. The 1H NMR data are as follows: 1 H NMR(400MHz, CDCl 3 , δ ppm): 7.2 - 7.8 (24H, benzene ring); 3.32 (4H, -N-CH 2 -); 1.29 (8H, -CH 2 -); 2.31 (4H, -CH 2 -COO-); 1.20 (18H, -CH 3 ).

[0137] S15. Add intermediate IV and 4-aminophthalic acid to anhydrous tetrahydrofuran, heat under reflux for 16 h, and then use Ehrlich's reagent to confirm the end point of the reaction. After the reaction is completed, add a saturated sodium chloride solution, let it stand, insoluble substances will be produced. Filter to obtain the insoluble substances, wash them with deionized water, and dry them in vacuo at 40 °C for 8 h to obtain intermediate V.

[0138] The dosage ratio of intermediate IV, 4-aminophthalic acid, anhydrous tetrahydrofuran, saturated sodium chloride solution, and deionized water is 0.1 mol: 0.12 mol: 200 mL: 300 mL: 500 mL.

[0139] Its 1H NMR spectrum is shown in Figure 5 as follows. The 1H NMR data are as follows: 1 H NMR(400MHz, CDCl 3 , δ ppm): 7.2 - 8.0 (27H, benzene ring); 12.0 - 12.1 (2H, -COOH); 11.23 (1H, -NH-); 3.32 (4H, -N-CH 2 -); 1.29 (8H, -CH 2 -); 2.31 (4H, -CH 2 -COO-); 1.20 (18H, -CH 3 ).

[0140] S16. Add intermediate V and tetrapod-like zinc oxide whiskers to anhydrous acetone, stir magnetically at 85 °C for 2.5 h, then pour the mixed solution into a petri dish and dry it in vacuo at 100 °C for 48 h to obtain an organic-inorganic hybrid light conversion agent.

[0141] The dosage ratio of intermediate V, tetrapod-like zinc oxide whiskers, and anhydrous acetone is 1.0 g: 10 g: 200 mL.

[0142] Its 1H NMR spectrum is shown in Figure 6 as follows. The 1H NMR data are as follows: 1 H NMR (400 MHz, δ ppm): 7.2 - 8.0 (27H, benzene ring); 11.23 (1H, -NH-); 3.32 (4H, -N-CH 2 -); 1.29 (8H, -CH 2 -); 2.31 (4H, -CH 2 -COO-); 1.20 (18H, -CH 3 ).

[0143] An EVA light conversion film comprises raw materials in the following parts by weight:

[0144] 100 parts of EVA resin;

[0145] 1.0 part of crosslinking agent;

[0146] 2.0 parts of co-crosslinking agent;

[0147] 6.0 parts of organic-inorganic hybrid light conversion agent;

[0148] 0.2 part of antioxidant;

[0149] 0.2 part of light stabilizer;

[0150] 0.4 part of coupling agent.

[0151] Example 2

[0152] A preparation method of an organic-inorganic hybrid light conversion agent comprises the following steps:

[0153] S11, adding benzotriazole into hydrobromic acid, stirring, slowly dropping liquid bromine into the reaction system, heating under reflux for 18 h; quenching with saturated aqueous sodium bisulfite solution, extracting with dichloromethane, separating the liquid, taking the organic phase, drying with anhydrous sodium sulfate, filtering, taking the solution, separating by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and drying in vacuum at 40 °C for 8 h to obtain intermediate I;

[0154] The dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated aqueous sodium bisulfite solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.15 mol: 400 mL: 300 mL: 5 g.

[0155] S12. Take the intermediate I, potassium carbonate, tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 60 °C for 40 h. After the reaction is completed, cool to room temperature, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry under vacuum at 40 °C for 8 h to obtain intermediate II.

[0156] The dosage ratio of intermediate I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.12 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0157] S13. Mix intermediate II, 4-(phenylamino)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium, then add them to a reactor, N 2 Replace the protection; after adding the mixed solvent, stir and reflux for 12 h; add deionized water and shake, extract with dichloromethane, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry under vacuum at 40 °C for 8 h to obtain intermediate III.

[0158] The dosage ratio of intermediate II, 4-(phenylamino)phenylboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.16 mol: 0.5 mol: 0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0159] The mixed solvent is a mixture of toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0160] S14. Purge the reaction system with N2 to displace the gas and protect it with nitrogen. Add intermediate III to tetrahydrofuran A, stir magnetically, add n-butyllithium, cool in an ice bath, stir for 15 min, then drip it into tetrahydrofuran B containing 2,4,6-trichloro-1,3,5-triazine using a peristaltic pump. After the addition is completed, reflux and react for 8 h; cool to room temperature, inject deionized water, stir for 15 min to obtain an insoluble substance, filter to obtain the insoluble substance, recrystallize with dichloromethane and n-hexane, and dry under vacuum at 40 °C for 8 h to obtain intermediate IV.

[0161] The dosage ratio of intermediate III, tetrahydrofuran A, n-butyllithium, 2,4,6-trichloro-1,3,5-triazine, tetrahydrofuran B, and deionized water is 0.20 mol: 200 mL: 0.20 mol: 0.1 mol: 300 mL: 800 mL.

[0162] S15. Add the intermediate product IV and 4-aminophthalic acid into anhydrous tetrahydrofuran, heat under reflux for 10 h, and then use Ehrlich's reagent to confirm the end point of the reaction. After the reaction is completed, add saturated saline solution, let it stand, insoluble substances will be produced. Filter to obtain the insoluble substances, wash them with deionized water, and dry them under vacuum at 40 °C for 8 h to obtain intermediate product V.

[0163] The dosage ratio of intermediate product IV, 4-aminophthalic acid, anhydrous tetrahydrofuran, saturated saline solution, and deionized water is 0.1 mol: 0.12 mol: 200 mL: 300 mL: 500 mL.

[0164] S16. Add intermediate product V and tetrapod-like zinc oxide whiskers into anhydrous acetone, stir magnetically at 90 °C for 2 h, then pour the mixed solution into a petri dish and dry it under vacuum at 100 °C for 48 h to obtain intermediate product V, namely the organic-inorganic hybrid light conversion agent.

[0165] The dosage ratio of intermediate product V, tetrapod-like zinc oxide whiskers, and anhydrous acetone is 1.0 g: 10 g: 200 mL.

[0166] An EVA light conversion film comprises raw materials in the following weight parts:

[0167] EVA resin: 100 parts;

[0168] Crosslinking agent: 0.5 part;

[0169] Co-crosslinking agent: 3.0 parts;

[0170] Organic-inorganic hybrid light conversion agent: 6.0 parts;

[0171] Antioxidant: 0.2 part;

[0172] Light stabilizer: 0.2 part;

[0173] Coupling agent: 0.3 part.

[0174] Example 3

[0175] A preparation method of an organic-inorganic hybrid light conversion agent, comprising the following steps:

[0176] S11. Add benzotriazole into hydrobromic acid, stir, slowly drop liquid bromine into the reaction system, and heat under reflux for 24 h. Then add saturated aqueous sodium bisulfite solution to quench, extract with dichloromethane, separate the layers, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it under vacuum at 40 °C for 8 h to obtain intermediate product I.

[0177] The dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated aqueous sodium bisulfite solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.12 mol: 400 mL: 300 mL: 5 g.

[0178] S12. Take intermediate I, potassium carbonate, and tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 40 °C for 48 h. After the reaction is completed, cool to room temperature, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the liquid, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and vacuum dry at 40 °C for 8 h to obtain intermediate II.

[0179] The dosage ratio of intermediate I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.15 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0180] S13. Mix intermediate II, 4-(phenylamino)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium, then add them to a reactor, N 2 Replace the protection; after adding the mixed solvent, stir and reflux for 24 h; add deionized water and shake, extract with dichloromethane, separate the liquid, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40 °C for 8 h to obtain intermediate III.

[0181] The dosage ratio of intermediate II, 4-(phenylamino)phenylboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.12 mol: 0.5 mol: 0.005 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0182] The mixed solvent is a mixture of toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0183] S14. Purge the reaction system with N 2 Replace the gas and protect with nitrogen. Add intermediate III to tetrahydrofuran A, stir magnetically, add n-butyllithium, cool in an ice bath, stir for 15 min, then slowly add it dropwise to tetrahydrofuran B containing 2,4,6-trichloro-1,3,5-triazine using a peristaltic pump. After the addition is complete, heat and reflux for 5 h; cool to room temperature, inject deionized water, stir for 15 min to obtain an insoluble substance, filter to obtain the insoluble substance, recrystallize with dichloromethane and n-hexane, and vacuum dry at 40 °C for 8 h to obtain intermediate IV.

[0184] The dosage ratio of intermediate III, tetrahydrofuran A, n-butyllithium, 2,4,6-trichloro-1,3,5-triazine, tetrahydrofuran B, and deionized water is 0.22 mol: 200 mL: 0.25 mol: 0.1 mol: 300 mL: 800 mL.

[0185] S15. Take intermediate IV and 4-aminophthalic acid and add them to anhydrous tetrahydrofuran. After heating under reflux for 20 h, use Ehrlich's reagent to confirm the end point of the reaction; after the reaction is completed, add a saturated sodium chloride solution, let it stand, insoluble substances are produced, filter to obtain the insoluble substances, wash them with deionized water, and vacuum dry them at 40 °C for 8 h to obtain intermediate V.

[0186] The dosage ratio of intermediate IV, 4-aminophthalic acid, anhydrous tetrahydrofuran, saturated sodium chloride solution, and deionized water is 0.1 mol: 0.1 mol: 200 mL: 300 mL: 500 mL.

[0187] S16. Add intermediate V and tetrapod-like zinc oxide whiskers to anhydrous acetone. After magnetic stirring at 80 °C for 3 h, pour the mixed solution into a petri dish and vacuum dry it at 100 °C for 48 h to obtain an organic-inorganic hybrid light conversion agent.

[0188] The dosage ratio of intermediate V, tetrapod-like zinc oxide whiskers, and anhydrous acetone is 1.0 g: 10 g: 200 mL.

[0189] An EVA light conversion film comprises raw materials in the following parts by weight:

[0190] 100 parts of EVA resin;

[0191] 1.5 parts of crosslinking agent;

[0192] 1.0 part of co-crosslinking agent;

[0193] 6.0 parts of organic-inorganic hybrid light conversion agent;

[0194] 0.2 part of antioxidant;

[0195] 0.2 part of light stabilizer;

[0196] 0.5 part of coupling agent.

[0197] Example 4

[0198] Others are the same as in Example 1, except that:

[0199] A preparation method of an organic-inorganic hybrid light conversion agent. In S15, 4-aminophthalic acid is replaced with p-aminobenzoic acid.

[0200] Example 5

[0201] Others are the same as those in Example 1, except that:

[0202] In the preparation method of an organic-inorganic hybrid light conversion agent, in S15, 4-aminophthalic acid is replaced with 1-aminobenzene-3,4,5-tricarboxylic acid.

[0203] Example 6

[0204] Others are the same as those in Example 1, except that:

[0205] In the preparation method of an organic-inorganic hybrid light conversion agent, in S16, the dosage ratio of intermediate V, tetrapod-like zinc oxide whiskers, and anhydrous acetone is 0.5 g: 10 g: 200 mL.

[0206] Example 7

[0207] Others are the same as those in Example 1, except that:

[0208] In the preparation method of an organic-inorganic hybrid light conversion agent, in S16, the dosage ratio of intermediate V, tetrapod-like zinc oxide whiskers, and anhydrous acetone is 2.0 g: 10 g: 200 mL.

[0209] Example 8

[0210] Others are the same as those in Example 1, except that:

[0211] In the preparation method of an organic-inorganic hybrid light conversion agent, in S16, tetrapod-like zinc oxide whiskers are replaced with titanium oxide whiskers.

[0212] Example 9

[0213] Others are the same as those in Example 1, except that:

[0214] In the preparation method of an organic-inorganic hybrid light conversion agent, in S16, tetrapod-like zinc oxide whiskers are replaced with copper oxide whiskers.

[0215] Example 10

[0216] Others are the same as those in Example 1, except that:

[0217] An EVA light conversion film, comprising the following raw materials in parts by weight:

[0218] EVA resin 100 parts;

[0219] Crosslinking agent 1.0 part;

[0220] Co-crosslinking agent 2.0 parts;

[0221] Organic-inorganic hybrid light conversion agent 6.0 parts;

[0222] Antioxidant: 0.1 part;

[0223] Light stabilizer: 0.3 part;

[0224] Coupling agent: 0.4 part.

[0225] Example 11

[0226] Others are the same as in Example 1, the difference is that:

[0227] An EVA light conversion film comprises the following raw materials in parts by weight:

[0228] EVA resin: 100 parts;

[0229] Crosslinking agent: 1.0 part;

[0230] Co-crosslinking agent: 2.0 parts;

[0231] Organic-inorganic hybrid light conversion agent: 6.0 parts;

[0232] Antioxidant: 0.25 part;

[0233] Light stabilizer: 0.1 part;

[0234] Coupling agent: 0.4 part.

[0235] Example 12

[0236] Others are the same as in Example 1, the difference is that:

[0237] An EVA light conversion film comprises the following raw materials in parts by weight:

[0238] EVA resin: 100 parts;

[0239] Crosslinking agent: 1.0 part;

[0240] Co-crosslinking agent: 2.0 parts;

[0241] Organic-inorganic hybrid light conversion agent: 2.0 parts;

[0242] Antioxidant: 0.2 part;

[0243] Light stabilizer: 0.2 part;

[0244] Coupling agent: 0.4 part.

[0245] Example 13

[0246] Others are the same as in Example 1, the difference is that:

[0247] An EVA light conversion film comprises the following raw materials in parts by weight:

[0248] EVA resin: 100 parts;

[0249] Crosslinking agent: 1.0 part;

[0250] Co-crosslinking agent: 2.0 parts;

[0251] Organic-inorganic hybrid light conversion agent: 10.0 parts;

[0252] Antioxidant: 0.2 part;

[0253] Light stabilizer: 0.2 part;

[0254] Coupling agent: 0.4 part.

[0255] Example 14

[0256] Others are the same as in Example 1, except that:

[0257] A POE encapsulating light conversion film, comprising the following raw materials in parts by weight:

[0258] POE resin: 100 parts;

[0259] Crosslinking agent: 1.0 part;

[0260] Co-crosslinking agent: 2.0 parts;

[0261] Organic-inorganic hybrid light conversion agent: 6.0 parts;

[0262] Antioxidant: 0.05 part;

[0263] Light stabilizer: 0.05 part;

[0264] Coupling agent: 0.8 part.

[0265] Example 15

[0266] Others are the same as in Example 1, except that:

[0267] An EPE encapsulating light conversion film, comprising an EVA layer (thickness 100 μm) and a POE layer (thickness 300 μm),

[0268] The EVA layer comprises the following raw materials in parts by weight:

[0269] EVA resin: 100 parts;

[0270] Crosslinking agent: 1.0 part;

[0271] Co-crosslinking agent: 2.0 parts;

[0272] Organic-inorganic hybrid light conversion agent: 6.0 parts;

[0273] Antioxidant: 0.2 part;

[0274] 0.2 parts of light stabilizer;

[0275] 0.4 parts of coupling agent.

[0276] A POE encapsulating light conversion film, comprising the following raw materials in parts by weight:

[0277] 100 parts of POE resin;

[0278] 1.0 part of crosslinking agent;

[0279] 2.0 parts of co-crosslinking agent;

[0280] 6.0 parts of organic-inorganic hybrid light conversion agent;

[0281] 0.05 part of antioxidant;

[0282] 0.05 part of light stabilizer;

[0283] 0.8 part of coupling agent.

[0284] The following comparative examples are all compared with Example 1:

[0285] Comparative Example 1

[0286] Others are the same as Example 1, the difference is that:

[0287] An organic-inorganic hybrid light conversion agent is not added to an EVA light conversion film formulation.

[0288] Comparative Example 2

[0289] Others are the same as Example 1, the difference is that:

[0290] A preparation method of an organic-inorganic hybrid light conversion agent, S14, the reaction system is purged with N 2 Replace the gas and protect it with nitrogen. Add the intermediate III to toluene A, stir magnetically, add palladium acetate and tert-butylphosphine, stir for 15 min, then dropwise add it to toluene B containing 1,3,5-tribromobenzene with a peristaltic pump, heat under reflux for reaction. After the dropping is completed, continue the reaction for 3 h; cool to room temperature, distill under reduced pressure, and vacuum dry at 40 °C for 8 h to obtain the intermediate IV.

[0291] The dosage ratio of the intermediate III, toluene A, palladium acetate, tert-butylphosphine, 1,3,5-tribromobenzene, and toluene B is 0.22 mol: 200 mL: 1.1 mmol: 0.25 mol: 0.1 mol: 300 mL.

[0292] S15. Take intermediate product IV and 4-aminophthalic acid and add them to toluene. After heating under reflux for 3 h, use Ehrlich's reagent to confirm the end point of the reaction. After the reaction is completed, add a saturated sodium chloride solution, let it stand, insoluble substances are produced, filter to obtain the insoluble substances, wash them with deionized water, and dry them under vacuum at 40 °C for 8 h to obtain intermediate product V.

[0293] The dosage ratio of intermediate product IV, 4-aminophthalic acid, toluene, saturated sodium chloride solution, and deionized water is 0.1 mol: 0.12 mol: 200 mL: 300 mL: 500 mL.

[0294] Comparative Example 3

[0295] Other conditions are the same as those in Comparative Example 1, except that:

[0296] A preparation method of an organic-inorganic hybrid light conversion agent, comprising the following steps:

[0297] S14. Pass N 2 Replace the gas and protect it with nitrogen. Add intermediate product III to N,N-dimethylformamide A, and use a peristaltic pump to drop it into N,N-dimethylformamide B containing 2,4,6-tribromomethyl-1,3,5-triazine and potassium carbonate. Heat to 100 °C and reflux for reaction. After the dropping is completed, continue the reaction for 8 h. Then cool to room temperature, distill under reduced pressure, and dry under vacuum at 40 °C for 8 h to obtain intermediate product IV.

[0298] The dosage ratio of intermediate product III, N,N-dimethylformamide A, 2,4,6-tribromomethyl-1,3,5-triazine, potassium carbonate, and N,N-dimethylformamide B is 0.22 mol: 200 mL: 0.1 mol: 0.25 mol: 300 mL.

[0299] S15. Take intermediate product IV, 4-aminophthalic acid, and potassium carbonate and add them to N,N-dimethylformamide. Heat to 100 °C and reflux for 6 h, then use Ehrlich's reagent to confirm the end point of the reaction. After the reaction is completed, concentrate by distillation under reduced pressure. Add a saturated sodium chloride solution to the concentrate, let it stand, insoluble substances are produced, filter to obtain the insoluble substances, wash them with deionized water, and dry them under vacuum at 40 °C for 8 h to obtain intermediate product V.

[0300] The dosage ratio of intermediate product IV, 4-aminophthalic acid, potassium carbonate, N,N-dimethylformamide, saturated sodium chloride solution, and deionized water is 0.1 mol: 0.12 mol: 0.12 mol: 200 mL: 300 mL: 500 mL.

[0301] Comparative Example 4

[0302] Other conditions are the same as those in Example 1, except that:

[0303] A preparation method of an organic-inorganic hybrid light conversion agent. In S12,

[0304] replace tert-butyl 5-bromovalerate with bromobutane.

[0305] Comparative Example 5

[0306] Other conditions are the same as in Example 1, except that:

[0307] In an EVA light conversion film formulation, replace the organic-inorganic hybrid light conversion agent with Intermediate V.

[0308] Comparative Example 6

[0309] Other conditions are the same as in Example 1, except that:

[0310] A preparation method of an organic-inorganic hybrid light conversion agent. In S16, replace tetrapod-like zinc oxide whiskers with spherical zinc oxide (average particle size is 50 nm);

[0311] Spherical zinc oxide, product number Brofos-ZnO-50, is purchased from Bohuasi Nano-Technology (Ningbo) Co., Ltd.

[0312] Comparative Example 7

[0313] Other conditions are the same as in Example 1, except that:

[0314] In an EVA light conversion film formulation, replace the organic-inorganic hybrid light conversion agent with a mixture of Intermediate V and tetrapod-like zinc oxide whiskers added in a dosage ratio of 1.0 g:10 g.

[0315] Measure the physical properties of the EVA light conversion films prepared in the examples and comparative examples of the present invention respectively. The results are shown in Table 1.

[0316]

[0317] First of all, it can be concluded from Examples 1-15 in Table 1 that the organic-inorganic hybrid light conversion agent and light conversion film for photovoltaics of the present invention have obvious advantages in improving properties such as photoelectric conversion efficiency, and at the same time have better anti-aging performance (stability).

[0318] Second, it can be observed from Example 1 and Comparative Example 1 that the light conversion film in the present invention using the self-made organic-inorganic hybrid light conversion agent has excellent light conversion efficiency. It can be observed from Example 1 and Comparative Examples 2-4 that the EVA film in the present invention uses the self-made organic-inorganic hybrid light conversion agent, and the triazine structure has a higher full width at half maximum and light conversion efficiency compared with the benzene ring bonding; the direct bonding of rigid groups can further improve the light conversion efficiency; in addition, the long-chain ester group structure can improve the compatibility and further improve the comprehensive performance; it can be observed from Example 1 and Comparative Examples 5-6 that the enrichment of the inorganic whisker structure in the organic-inorganic hybrid light conversion agent has a significant effect on improving the light conversion efficiency; and it has low migration performance; it can be observed from Example 1 and Comparative Example 7 that compared with simple physical blending, the light conversion efficiency, low migration and photoelectric gain effects of the organic-inorganic hybrid light conversion agent structure with the organic light conversion structure modifying the surface of the inorganic photosensitive metal oxide have obvious advantages.

[0319] Third, it can be observed from the examples that the light conversion film in the present invention has a persistent high light conversion efficiency, and thus should have excellent optical properties and stability.

[0320] In summary, the organic-inorganic hybrid light conversion agent and light conversion film for photovoltaic use in the present invention using the self-made light conversion agent have excellent light conversion performance, low migration, high stability and power gain function, etc.

[0321] The test methods are as follows:

[0322] (1) Full width at half maximum of absorption: Test the fluorescence excitation spectrum of the light conversion film.

[0323] (2) Light conversion efficiency: Use the Horiba spectrometer FL-3 to perform absolute quantum efficiency test with an integrating sphere at room temperature.

[0324] (3) Resistance to damp heat aging: Conduct a damp heat aging test on the film. Conditions: Test conditions: +85°C, relative humidity 85%.

[0325] Measure before and after the test, and calculate the retention rate according to the following formula:

[0326] Retention rate = average value after test / average value before test × 100%.

[0327] (4) Resistance to ultraviolet aging: Irradiate the obtained film with ultraviolet rays according to the requirements specified in the International Electrotechnical Commission standard IEC61345. Test conditions: The surface temperature of the test piece is 60 ± 5°C, the ultraviolet wavelength range is 280 - 400 nm, and the irradiation intensity is 15 kW·h / m 2 , and the ultraviolet irradiation test time is 2000 hr.

[0328] Measure before and after the test, and calculate the retention rate according to the following formula:

[0329] Retention rate = Average value after test / Average value before test × 100%.

[0330] (5) Migration rate test method: Conduct a rapid aging migration test at the component end. The front side of the photovoltaic module is a light conversion film doped with a light conversion agent, and the back side of the module is a blank film without a light conversion agent (only the light conversion agent is the variable). After the module undergoes a UV300 aging experiment in an aging chamber, the adhesive film on the front side of the module is removed and subjected to heating and soaking treatment with an organic solvent (methanol) (stirring, heating and soaking at 60°C for 24H). The solution after soaking is analyzed by HPLC to obtain the content (A) of one example. Remove the adhesive film on the front side of the unaged module, conduct the same heating and soaking treatment, and analyze the solution after soaking by HPLC to obtain the content (B) of another example. The migration rate is: A / B * 100%.

[0331] (6) Photoelectric gain: Measured using an EL tester. Stack the photovoltaic glass, adhesive film, cell, adhesive film, and photovoltaic backplane neatly from top to bottom, laminate at 140°C for 15 min, take out and cool. First, test the power of the bare chip and record it as P 0.1 ; Use the adhesive film without an adsorbent to laminate to obtain a module, test its power, and record it as P 1 ; Test the power of the new bare chip and record it as P 0.2 , laminate using the adhesive film in the present invention, test its power, and record it as P 2 , then the power gain P m = (P 2 / P 0.2 ) / (P 1 / P 0.1 ).

[0332] Taking the ideal embodiments according to the present invention as an inspiration, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. An organic-inorganic hybrid light conversion agent, characterized in that: The structural formula is shown below: ； Wherein, M is Zn.

2. A method for preparing the organic-inorganic hybrid light conversion agent as claimed in claim 1, characterized in that: The following steps are involved: S11, adding benzotriazole to hydrobromic acid, stirring, slowly adding liquid bromine to the reaction system, heating and refluxing for 20 hours, adding saturated sodium bisulfite aqueous solution to quench, extracting with dichloromethane, separating the liquids, taking the organic phase, adding anhydrous sodium sulfate to dry, filtering, taking the solution, separating by column chromatography, using an eluent of petroleum ether and dichloromethane in a volume ratio of 1 / 10, and vacuum drying at 40°C for 8 hours to obtain intermediate product I; The usage ratio of the benzotriazole, the hydrobromic acid, the liquid bromine, the saturated sodium bisulfite aqueous solution, the dichloromethane, and the anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.14 mol: 400 mL: 300 mL: 5 g; S12, taking the intermediate product I, potassium carbonate, and tert-butyl 5-bromovalerate, adding them to N,N-dimethylformamide, stirring and heating at 50° C. for 46 hours, cooling to room temperature after the reaction, washing with saturated ammonium chloride solution three times, extracting with ethyl acetate, separating the liquids, taking the organic phase, adding anhydrous sodium sulfate to dry, filtering, taking the solution, separating by column chromatography, using an eluent of petroleum ether and dichloromethane in a volume ratio of 1 / 5, and vacuum drying at 40° C. for 8 hours to obtain an intermediate product II; The usage ratio of the intermediate product I, the potassium carbonate, the tert-butyl 5-bromovalerate, the N,N-dimethylformamide, the saturated ammonium chloride solution, the ethyl acetate, and the anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.14 mol: 200 mL: 300 mL: 400 mL: 5 g; S13, taking the intermediate product II, 4-(aniline)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium, mixing them and adding them to a reactor, and performing N2 replacement protection; adding a mixed solvent, stirring, and heating under reflux for 20 hours; adding deionized water for oscillation, extracting with dichloromethane, separating the liquids, taking the organic phase, adding anhydrous sodium sulfate for drying, filtering, taking the solution, and separating it by column chromatography, using an eluent of petroleum ether and dichloromethane in a volume ratio of 1 / 10, and vacuum drying at 40° C. for 8 hours to obtain an intermediate product III; The usage ratio of the intermediate product II, the 4-(aniline)phenylboric acid, the potassium carbonate, the tetrakis(triphenylphosphine)palladium, the mixed solvent, the deionized water, the dichloromethane, and the anhydrous sodium sulfate is 0.1 mol: 0.14 mol: 0.5 mol: 0.008 mol: 150 mL: 200 mL: 300 mL: 5 g; The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1; S14, the reaction system is passed through N2 to replace the gas and protected by nitrogen, the intermediate product III is added to tetrahydrofuran A, magnetically stirred, n-butyl lithium is added, ice bath is placed, stirred for 15 minutes, and then added dropwise to tetrahydrofuran B containing 2,4,6-trichloro-1,3,5-triazine using a peristaltic pump. After the addition is completed, the mixture is heated under reflux for 6 hours; cooled to room temperature, deionized water is injected, stirred for 15 minutes, insoluble matter is obtained, the insoluble matter is filtered out, recrystallized with dichloromethane and n-hexane, and vacuum dried at 40° C. for 8 hours to obtain an intermediate product IV; The usage ratio of the intermediate product III, the tetrahydrofuran A, the n-butyl lithium, the 2,4,6-trichloro-1,3,5-triazine, the tetrahydrofuran B, and the deionized water is 0.22 mol: 200 mL: 0.22 mol: 0.1 mol: 300 mL: 800 mL; S15, taking the intermediate product IV and 4-aminophthalic acid, adding them to anhydrous tetrahydrofuran, heating and refluxing for 16 hours, and confirming the reaction endpoint using Ehrlich reagent; after the reaction, adding saturated saline solution, standing to produce insoluble matter, filtering the insoluble matter, eluting with deionized water, and vacuum drying at 40° C. for 8 hours to obtain an intermediate product V; The usage ratio of the intermediate product IV, the 4-aminophthalic acid, the anhydrous tetrahydrofuran, the saturated saline solution, and the deionized water is 0.1 mol: 0.12 mol: 200 mL: 300 mL: 500 mL; S16, adding the intermediate product V and the tetrapod-shaped zinc oxide whisker to anhydrous acetone, stirring under magnetic force at 85° C. for 2.5 h, introducing the mixed solution into a watch glass, and vacuum drying at 100° C. for 48 h to obtain an organic-inorganic hybrid light conversion agent; The usage ratio of the intermediate product V, the four-needle zinc oxide whisker, and the anhydrous acetone is 1.0 g:10 g:200 mL.

3. A light-converting adhesive film, characterized in that: It comprises the organic-inorganic hybrid light conversion agent as claimed in claim 1.

4. The light-converting adhesive film according to claim 3, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of polyolefin resin; Cross-linking agent 0.5-1.5 parts; 1.0-3.0 parts of auxiliary cross-linking agent; 2.0-10.0 parts of the organic-inorganic hybrid light conversion agent; Antioxidant 0.05-0.25 parts; Light stabilizer 0.05-0.3 parts; Coupling agent 0.3-0.8 parts.

5. The light-converting adhesive film according to claim 4, characterized in that: The polyolefin resin is selected from at least one of EVA resin and POE resin.

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