Organic-inorganic hybrid light conversion agent, preparation method and light conversion adhesive film

Abstract

The invention belongs to the technical field of photovoltaic adhesive films, and particularly relates to an organic-inorganic hybrid light conversion agent, a preparation method and a light conversion adhesive film. The organic-inorganic hybrid light conversion agent is formed by chemical bonding of an organic light conversion agent and a surface-modified inorganic light conversion agent, the organic light conversion agent is 7-(R1-N-R2)-4-methylcoumarin containing carbon-carbon double bonds or siloxane groups, the surface-modified inorganic light conversion agent is inorganic fluorescent powder coated with a silane coupling agent layer on the surface, and the silane coupling agent layer is a silane coupling agent layer on the surface of the inorganic fluorescent powder. A bonding structure is formed by chemical bonding of a carbon-carbon double bond or a siloxane group in the organic light conversion agent and a surface coating layer silane coupling agent of the surface modified inorganic light conversion agent, so that the optical performance of the adhesive film is further improved by utilizing a fluorescence resonance energy transfer effect; and the adhesive film can be bonded in a polymer network of the adhesive film through chemical bonds to improve the stability and aging resistance of the adhesive film, so that the efficiency gain of the photovoltaic module is improved and the service life of the photovoltaic module is prolonged.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of compound preparation, and more particularly relates to an organic-inorganic hybrid light conversion agent, a preparation method thereof, and a light conversion adhesive film. BACKGROUND

[0002] With the development of photovoltaic cell technology, heterojunction (HJT) cells have attracted much attention in the industry due to their symmetrical structure, simple process, and considerable efficiency. However, the passivation layer on the surface of the cell is sensitive to ultraviolet light, which can easily cause photoaging and thus damage the cell and reduce the power of the module. To protect the HJT cell, improve the reliability of the module, increase the utilization rate of solar spectrum, and increase the photoelectric conversion efficiency of the module, it is urgent to develop a light conversion adhesive film that can convert ultraviolet light into visible light.

[0003] The key to preparing the light conversion adhesive film lies in the use of a special light conversion agent. The light conversion agent can be selected from organic light-emitting compounds, such as organic light-emitting rare earth compounds and organic dyes. However, the stability of organic light conversion agents is not good, and there is a risk of a decrease in light conversion ability over a long period of time.

[0004] In addition to organic light conversion agents, another type of light conversion agent that can be selected is an inorganic compound, such as an inorganic rare earth compound or an inorganic fluorescent powder. However, there are dispersion and compatibility problems when it is used. Existing solutions to the dispersion and compatibility of inorganic light conversion agents include: making master batches (CN117467167A) and surface coating technology (CN104194661A). Making master batches by pre-mixing inorganic fluorescent light conversion agents with polymers into master batches helps to improve the uniform dispersion of the light conversion agent in the matrix and simplifies subsequent processing. Surface coating technology further improves the dispersion, compatibility and stability of the inorganic light conversion agent in the matrix by coating a layer of organic or inorganic material, such as silicon dioxide or a polymer layer, on the surface of the inorganic light conversion agent, while providing better weather resistance and light stability to prevent the aggregation and light performance degradation of the inorganic light conversion agent. However, the above-mentioned solutions have the problems of: complex process, environmental unfriendliness, and instability of the light conversion agent in the photovoltaic adhesive film. SUMMARY

[0005] Therefore, the present application aims to provide an organic-inorganic hybrid light conversion agent with high light conversion stability and good compatibility with the matrix resin, a preparation method thereof, and a light conversion adhesive film.

[0006] To solve the above technical problems, the present application adopts the following technical solutions:

[0007] The organic-inorganic hybrid light conversion agent according to the first aspect of the present application is formed by chemical bonding of an organic light conversion agent and a surface-modified inorganic light conversion agent;

[0008] The organic light-converting agent is 7-(R1-N-R2)-4-methylcoumarin, wherein at least one of the substituents in R1 and R2 contains a carbon-carbon double bond or a siloxane group.

[0009] The surface-modified inorganic light-converting agent is an inorganic phosphor with a silane coupling agent layer coated on its surface.

[0010] According to some embodiments of the present invention, the substituent group containing the carbon-carbon double bond is an alkenyl group, an alkenyl group containing heteroatoms, a cycloalkenyl group, or a cycloalkenyl group containing heteroatoms;

[0011] The substituent containing the siloxane group is the substituent obtained by hydrosilylation of the substituent containing the carbon-carbon double bond with a siloxysilane.

[0012] According to some embodiments of the present invention, the siloxysilane is trimethoxysilane, triethoxysilane, methyldimethoxysilane, or methyldiethoxysilane.

[0013] According to some embodiments of the present invention, the mass ratio of organic light-converting agent to surface-modified inorganic light-converting agent is 1:(0.5-2).

[0014] According to some embodiments of the present invention, the silane coupling agent layer is composed of at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane;

[0015] or / and,

[0016] The inorganic phosphor is at least one of nitride phosphor and oxide phosphor;

[0017] or / and,

[0018] The mass ratio of the silane coupling agent layer to the inorganic phosphor is (0.005-0.1):1.

[0019] According to a second aspect of the present invention, a method for preparing an organic-inorganic hybrid light-converting agent according to any embodiment of the first aspect is provided, comprising the following steps:

[0020] Inorganic phosphors were dispersed in an organic solvent, and a silane coupling agent was added. The mixture was stirred for 5–36 h. The reaction product was then collected, washed, and dried to obtain a surface-modified inorganic phosphor.

[0021] The organic light conversion agent is mixed with the surface-modified inorganic light conversion agent to perform a hybrid reaction, thereby obtaining an organic-inorganic hybrid light conversion agent.

[0022] According to some embodiments of the present application, at least the R2 substituent group of the organic light conversion agent comprises a carbon-carbon double bond or a siloxane group, which can be prepared by the following method:

[0023] Part of the hydrogen in the amino group of 7-amino-4-methylcoumarin is replaced by tosyl chloride to obtain (HN-Ts)-methylcoumarin;

[0024] (HN-Ts)-methylcoumarin is reacted with a compound introducing the R1 substituent group to form (R1-N-Ts)-methylcoumarin;

[0025] (R1-N-Ts)-methylcoumarin is subjected to a tosyl group removal reaction to obtain (R1-N-H)-methylcoumarin;

[0026] (R1-N-H)-methylcoumarin is subjected to a replacement reaction with a compound introducing the R2 substituent group containing a carbon-carbon double bond to form 7-(R1-N-R2)-4-methylcoumarin, wherein the R2 substituent group contains a carbon-carbon double bond;

[0027] Alternatively, 7-(R1-N-R2)-4-methylcoumarin, wherein the R2 substituent group contains a carbon-carbon double bond, is further subjected to a hydrosilylation reaction with a siloxysilane to form 7-(R1-N-R2)-4-methylcoumarin, wherein the R2 substituent group contains a siloxane group.

[0028] According to a third aspect of the present application, a light conversion adhesive film is provided, comprising, by weight:

[0029] a base resin, 70-99 parts;

[0030] the organic-inorganic hybrid light conversion agent of any one of the embodiments of the first aspect, 0.01-5 parts;

[0031] a crosslinking agent, 0.1-10 parts;

[0032] a co-crosslinking agent, 0.1-10 parts; and

[0033] a silane coupling agent, 0.1-10 parts.

[0034] According to some embodiments of the present application, the light conversion adhesive film further comprises other functional additives, 0.03-7 parts;

[0035] The other functional additives comprise at least one of a light stabilizer, an antioxidant, and an anti-aging agent.

[0036] According to some embodiments of the present application, the base resin is one or more of EVA, POE, PVB, PMMA, silicone resin;

[0037] or / and,

[0038] The crosslinking agent is at least one of any one or more of t-butyl peroxy-2-ethylhexyl carbonate, 1,1-bis(t-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl peroxy isopropyl carbonate, 1,1-bis(t-amylperoxy)cyclohexane, t-amyl peroxy-2-ethylhexyl carbonate, t-amyl peroxy carbonate, and t-butyl peroxy 3,3,5-trimethyl hexanoate;

[0039] or / and,

[0040] The co-crosslinking agent is at least one of glyceryl triacrylate propoxylate, triallyl-1,3,5-triazine-2,4,6-trione, trimethylolpropane triacrylate, triallyl isocyanurate, and polytriallyl isocyanurate;

[0041] or / and,

[0042] The silane coupling agent includes one or more of γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxysilane, and hexadecyl triethoxysilane;

[0043] The light stabilizer is one or both of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly(butylene succinate-4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidinoethanol);

[0044] or / and,

[0045] The antioxidant is selected from one or more of tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid octadecyl ester;

[0046] or / and,

[0047] The anti-aging agent is selected from one or both of 2,6-di-tert-butyl-p-cresol and alpha-tocopherol.

[0048] The above technical solutions of the present application have at least one of the following beneficial effects:

[0049] According to the organic-inorganic hybrid light conversion agent of the present application, the linking structure formed by chemical bonding between the carbon-carbon double bond or siloxane group in the organic light conversion agent and the silane coupling agent of the surface coating layer of the surface-modified inorganic light conversion agent not only helps to further improve the optical performance of the film by using the fluorescence resonance energy transfer effect, but also improves the stability and anti-aging property of the film by being chemically bonded in the polymer network of the film, thereby helping to improve the efficiency gain and service life of the photovoltaic module.

[0050] In addition, for the organic light conversion agent part, by introducing unsaturated bonds or siloxane groups, the light conversion agent can absorb photons in a wider ultraviolet light band, convert energy into visible light, and be chemically bonded in the polymer network of the film, thereby improving the photoelectric conversion efficiency and stability of the light conversion effect of the solar cell and improving the overall photoelectric conversion efficiency of the photovoltaic module; for the inorganic light conversion agent part, after surface modification, the inorganic light conversion agent can be chemically bonded with the organic light conversion agent, thereby improving its dispersibility and solving the problem of poor compatibility with the base resin. DETAILED DESCRIPTION

[0051] To make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present application.

[0052] I. Organic-inorganic hybrid light conversion agent and preparation method thereof

[0053] The organic-inorganic hybrid light conversion agent and the preparation method thereof according to the present application will be described in detail below.

[0054] For the purpose of facilitating understanding and simplification, the preparation method is described first, and the organic-inorganic hybrid light conversion agent is further described as the final target product of the preparation method.

[0055] It should be noted that the present application firstly proposes to hybridize the organic light conversion agent and the inorganic light conversion agent to obtain an organic-inorganic hybrid light conversion agent (i.e., a composite light conversion agent). The organic-inorganic hybrid light conversion agent of the present application is not specifically limited by the following preparation method, that is, the organic-inorganic hybrid light conversion agent of the present application can also be prepared by any other method, as long as it can be hybridized together to obtain the organic-inorganic hybrid light conversion agent of the present application.

[0056] According to the preparation method of the organic-inorganic hybrid light conversion agent of the present application, the method comprises:

[0057] Step S1, dispersing the inorganic fluorescent powder, deionized water and ammonia water in an organic solvent, and adding a silane coupling agent, stirring and reacting for 5-36 hours, then collecting the reaction product and washing and drying to obtain a surface-modified inorganic light conversion agent;

[0058] Step S2, mixing the organic light conversion agent and the surface-modified inorganic light conversion agent to carry out a hybridization reaction to obtain an organic-inorganic hybrid light conversion agent.

[0059] That is, according to the preparation method of the organic-inorganic hybrid light conversion agent of the present application, on the one hand, the substituent structure of the organic light conversion agent is designed to introduce a carbon-carbon double bond or a siloxane group; on the other hand, the inorganic light conversion agent is surface-modified, and then the organic light conversion agent containing the carbon-carbon double bond or the siloxane group is mixed with the surface-modified inorganic light conversion agent to hybridize, so as to obtain the organic-inorganic hybrid light conversion agent.

[0060] The specific selection and processing of the organic light conversion agent and the inorganic light conversion agent will be described in detail below.

[0061] (I) Organic light conversion agent

[0062] The inventors of the present application found through repeated research that by using methyl coumarin as a light-emitting core, introducing a carbon-carbon double bond or a siloxane group by designing a substituent structure, regulating the absorption of photons in a wide ultraviolet light band, converting energy into visible light, and being able to be chemically bonded in the polymer network of the film, the light-to-electricity conversion efficiency and the stability of the light conversion effect of the solar cell can be improved, and the overall light-to-electricity conversion efficiency of the photovoltaic module can be improved.

[0063] By optimizing the organic light conversion agent and introducing a carbon-carbon double bond or a siloxane group, on the one hand, the absorption of photons in a wide ultraviolet light band can be promoted to convert energy into visible light; on the other hand, the bonding with the inorganic light conversion agent can be promoted, and the light-to-electricity conversion efficiency and the stability of the light conversion effect of the solar cell can be improved by being chemically bonded in the polymer network of the film.

[0064] Specifically, the organic light-conversion agent can be 7-(R1-N-R2)-4-methyl coumarin, wherein at least one of R1 and R2 contains a carbon-carbon double bond or a siloxane group.

[0065] In some embodiments of the present application, the substituent containing a carbon-carbon double bond is an alkenyl group, a heteroatom-containing alkenyl group, a cycloalkenyl group or a heteroatom-containing cycloalkenyl group; and the substituent containing a siloxane group is a substituent obtained by hydrosilylation of the substituent containing a carbon-carbon double bond with a siloxy silane.

[0066] As an example, at least the R2 substituent contains a carbon-carbon double bond or a siloxane group, and accordingly, R1 can be selected from any substituent, such as an alkyl group, an alkenyl group, a cycloalkyl group, a heteroalkyl group, an aryl group, a heteroaryl group, an alkoxyalkyl group, a heteroalkenyl group, an arylalkyl group, a cycloalkenyl group, a cycloheteroalkyl group and a cycloheteroalkenyl group, etc.

[0067] When R2 is a substituent containing a carbon-carbon double bond, R2 can be selected from an alkenyl group, a heteroatom-containing alkenyl group, a cycloalkenyl group and a heteroatom-containing cycloalkenyl group.

[0068] When R2 is a substituent containing a siloxane group, the substituent containing a siloxane group is obtained by hydrosilylation of the substituent containing a carbon-carbon double bond with a siloxy silane, and the siloxy silane is trimethoxysilane, triethoxysilane, methyldimethoxysilane or methyldiethoxysilane.

[0069] That is, by introducing R1 and R2 into the methyl coumarin at the same time, and by introducing at least one of the carbon-carbon double bond or the siloxane group, not only can the photons be absorbed in a wider ultraviolet light band to convert the energy into visible light, but also the conversion rate can be improved. In particular, in the case of the combination of R1 and the siloxane group, the bonding stability with the inorganic fluorescent molecule conversion agent can be further improved.

[0070] When the R2 substituent in the organic light-conversion agent contains a carbon-carbon double bond, the organic light-conversion agent can be prepared by the following steps:

[0071] 1) displacing part of the hydrogen in the amino group of 7-amino-4-methyl coumarin with p-toluenesulfonyl chloride to obtain (HN-Ts)-methyl coumarin (Ts represents p-toluenesulfonyl group);

[0072] 2) reacting (HN-Ts)-methyl coumarin with a compound introducing the R1 group to generate (R1-N-Ts)-methyl coumarin;

[0073] 3) de-tosylating (R1-N-Ts)-methyl coumarin to obtain (R1-N-H)-methyl coumarin;

[0074] 4) substitution reaction of (R1-N-H)-methyl coumarin with a compound introducing R2 substituent containing carbon-carbon double bond to form 7-(R1-N-R2)-4-methyl coumarin with R2 substituent containing carbon-carbon double bond.

[0075] That is, its synthetic route is shown in the following formula (1):

[0076]

[0077] That is, first, the p-toluenesulfonyl group is used to replace half of the hydrogen on the amino group, then the R1 group is introduced to replace the remaining hydrogen, then the p-toluenesulfonyl group is removed, and finally the R2 substituent containing carbon-carbon double bond is introduced to form 7-(R1-N-R2)-4-methyl coumarin with R2 substituent containing carbon-carbon double bond.

[0078] In the case of R2 substituent containing siloxane group in the organic light-converting agent, the preparation of the organic light-converting agent is actually further carried out after the end of step 4) above, that is:

[0079] 5) silicohydrogenation reaction of 7-(R1-N-R2)-4-methyl coumarin with R2 substituent containing carbon-carbon double bond with siloxysilane to form 7-(R1-N-R2)-4-methyl coumarin with R2 substituent containing siloxane group.

[0080] Further, the silicohydrogenation reaction can be carried out in the presence of a catalyst, which can be selected from one or more of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum, chloroplatinic acid hexahydrate, platinum acetylacetone, and tris(triphenylphosphine) rhodium chloride.

[0081] Specifically, its synthetic route is shown in the following formula (2), where in order to distinguish whether the R2 substituent contains carbon-carbon double bond or siloxane group, only in formula (2) R2 represents the substituent containing carbon-carbon double bond and R2 ＇ represents the substituent containing siloxane group:

[0082]

[0083] After the above treatment, one or more carbon-carbon double bonds or siloxane groups are introduced on the basis of methyl coumarin as the light-emitting core. By designing the substituent in this way, the conversion of ultraviolet light to visible light can be achieved in a wider range, and when used in photovoltaic modules, the conversion efficiency can be effectively improved.

[0084] (B) Surface treatment of inorganic light-converting agent

[0085] The inventors of the present application have found through repeated research that by surface modification of inorganic fluorescent powder, the dispersibility of the inorganic fluorescent powder is improved, and the inorganic fluorescent powder can be bonded to organic light conversion agents and matrix resins through chemical bonds to form a more stable structure.

[0086] Specifically, the surface of the inorganic fluorescent powder can be surface modified by a silane coupling agent.

[0087] As the silane coupling agent, one or more of γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxysilane, and hexadecyl triethoxysilane can be selected.

[0088] Among them, as the inorganic fluorescent powder, nitride fluorescent powder, oxide fluorescent powder, or a mixture thereof can be selected.

[0089] In addition, as a specific method of surface treatment, for example, the following can be performed:

[0090] The inorganic fluorescent powder is dispersed in an organic solvent (such as ethanol, etc.) and a silane coupling agent is added, and the reaction is stirred for 5-36 hours to obtain a surface-modified inorganic light conversion agent.

[0091] Among them, deionized water can also be added to the organic solvent. The addition of deionized water can play the role of reaction medium and detergent, and can improve the purity of the light conversion agent and reduce light quenching.

[0092] In addition, a base such as ammonia can also be added to the organic solvent. In an alkaline environment, it can complex metal ions and catalyze hydrolysis, on the one hand, it can control the morphology of the surface-modified inorganic conversion agent particles, making the particle size more uniform, thereby enhancing the crystallinity and light-emitting efficiency.

[0093] In addition, by adding deionized water and a base, the hydrolysis of the silane coupling agent can be promoted, which is conducive to the adsorption of the silane coupling agent on the surface of the inorganic fluorescent powder to form a silane coupling agent layer.

[0094] Among them, the amount of silane coupling agent added is 0.5%-10% of the mass of the inorganic fluorescent powder. In the present application, by adding an excess amount of silane coupling agent, at least one layer of silane coupling agent molecular layer can be coated on the surface of the inorganic fluorescent powder.

[0095] The inorganic fluorescent powder is surface-modified by silane coupling agent, and then can be evenly filled into the long-chain gap of the base resin as an intermediate medium when applied to the light conversion adhesive film. In addition, the silane coupling agent on the surface of the surface-modified inorganic light conversion agent can not only form a chemical bond with the organic light conversion agent, but also crosslink with the crosslinking agent in the adhesive film to form a three-dimensional network that is insoluble and infusible, thereby fixing the position of the light conversion agent and obtaining an anti-aging and chemically stable light conversion adhesive film. The adhesive film is used to fix the solar cell and glass, and has the function of converting ultraviolet light into visible light, thereby improving the photoelectric conversion efficiency of the solar cell.

[0096] (III) Hybridization of organic-inorganic fluorescent light conversion agent

[0097] That is, after the organic light conversion agent is optimized and the inorganic light conversion agent is surface-modified, the two are mixed for hybridization to obtain an organic-inorganic hybrid light conversion agent.

[0098] Specifically, the organic light conversion agent (i.e., coumarin derivative containing carbon-carbon double bond or siloxane group) obtained in (I) above and the inorganic fluorescent powder surface-modified by silane coupling agent obtained in (II) above are mixed in a weight ratio of 1:(0.5-2) to obtain an organic-inorganic hybrid light conversion agent.

[0099] The organic-inorganic hybrid light conversion agent prepared by the above method uses the silane coupling agent layer on the surface of the surface-modified inorganic light conversion agent as a bridge, one end of which is bonded to the inorganic fluorescent powder and the other end is bonded to the organic light conversion agent, thereby forming a chemical bond structure. The organic light conversion agent part contains one or more carbon-carbon double bonds or siloxane groups through the design of the substituent group, which can realize the conversion of ultraviolet light to visible light in a wider range, and can effectively improve the conversion rate when used in photovoltaic components. For specific details of the carbon-carbon double bond or siloxane group, please refer to the above, and the detailed description is omitted here.

[0100] The organic-inorganic hybrid light conversion agent according to the embodiment of the present application has a structure that not only helps to further improve the efficiency gain of the battery component by using the fluorescence resonance energy transfer effect, but also can make the hybrid light conversion agent uniformly dispersed in the organic body (such as the base resin) to form a stable structure in a certain sense. Since the organic light conversion agent has a high fluorescence quantum yield and can efficiently absorb 200-400 nanometer ultraviolet light, the inorganic fluorescent powder generally has better photo-thermal stability and ultraviolet light resistance, which can significantly improve the anti-aging ability of the material. Therefore, the hybrid light conversion agent material can further improve the optical performance and chemical stability by using the fluorescence resonance energy transfer effect, and is particularly suitable for use in photovoltaic adhesive film to improve the ultraviolet light conversion efficiency and the service life of the component, thereby achieving better performance.

[0101] As described above, the organic-inorganic hybrid light conversion agent and the preparation method thereof according to the embodiments of the present application are described in detail.

[0102] The organic-inorganic hybrid light conversion agent according to the embodiments of the present application can be used to prepare a light conversion adhesive film, i.e. dispersed in a base resin, and then the base resin is cured to obtain the light conversion adhesive film.

[0103] In summary, the organic-inorganic hybrid light conversion agent and the preparation method thereof according to the embodiments of the present application are provided, which are simple, environmentally friendly, easy to operate and low in cost. The light conversion agent can be uniformly dispersed in the adhesive film and stably exist in the adhesive film for a long time, and can improve the ultraviolet light absorption rate and the visible light transmittance, and improve the light conversion efficiency and the overall photoelectric conversion efficiency of the photovoltaic module.

[0104] II. Light conversion adhesive film

[0105] The light conversion adhesive film is described below.

[0106] The light conversion adhesive film according to the embodiments of the present application can use the following components in parts by weight:

[0107] 70-99 parts of base resin;

[0108] 0.01-5 parts of the organic-inorganic hybrid light conversion agent provided in the above embodiments;

[0109] 0.1-10 parts of crosslinking agent;

[0110] 0.1-10 parts of co-crosslinking agent; and

[0111] 0.1-10 parts of silane coupling agent.

[0112] In addition, in order to improve the performance of the light conversion adhesive film, 0.03-7 parts of other functional additives can also be contained, wherein the other functional additives include at least one of light stabilizer, antioxidant and anti-aging agent.

[0113] In an example of the present application, for example, the other functional additives include:

[0114] 0.01-2 parts of light stabilizer;

[0115] 0.01-3 parts of antioxidant;

[0116] 0.01-2 parts of anti-aging agent.

[0117] The light conversion adhesive film according to the embodiment of the present application can be applied to the photovoltaic module for encapsulation to achieve better photoelectric conversion efficiency. As the base resin, one or more of EVA (ethylene-vinyl acetate copolymer), POE (polyolefin elastomer), PVB (polyvinyl butyral), PMMA (polymethyl methacrylate), and silicone resin can be selected.

[0118] In addition, as the specific film forming step, the organic-inorganic hybrid light conversion agent, crosslinking agent, co-crosslinking agent, silane coupling agent, and other functional additives can be added to the base resin for mixing, and then the film is formed by a film forming method to obtain the light conversion adhesive film.

[0119] As the film forming method, for example, the components such as the organic-inorganic hybrid light conversion agent and the base resin are stirred uniformly at a temperature of 20-50°C, the stirred semi-finished product is then left for 4-48h, and then is put into a screw extruder for screw extrusion at 70-120°C, and finally the light conversion adhesive film is formed by a flow casting method.

[0120] As the crosslinking agent, at least one of any one or more of t-butyl peroxy-2-ethylhexyl carbonate, 1,1-bis(t-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl peroxy isopropyl carbonate, 1,1-bis(t-amylperoxy)cyclohexane, t-amyl peroxy-2-ethylhexyl carbonate, t-amyl peroxy carbonate, and t-butyl peroxy-3,3,5-trimethylhexanoate can be selected.

[0121] As the co-crosslinking agent, one or more of glyceryl triacrylate propoxylate, 1,3,5-triallyl cyanurate, trimethylolpropane triacrylate, triallyl isocyanurate, and polytriallyl isocyanurate can be selected.

[0122] Further, the silane coupling agent includes one or more of γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxysilane, and hexadecyl triethoxysilane.

[0123] Further, for example, in order to improve light stability, a light stabilizer can be added. As the light stabilizer, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly(butylene succinate-4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidinoethanol), or a mixture thereof can be used.

[0124] In order to inhibit oxidative decomposition of the organic fluorescent molecule light conversion agent, an antioxidant can be added to the base resin. As the antioxidant, one or more of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester can be used.

[0125] In order to improve durability, an anti-aging agent can also be added. As the anti-aging agent, 2,6-di-tert-butyl-p-cresol, α-tocopherol, or a mixture thereof can be used.

[0126] Next, the hybrid light conversion agent according to the present application, the method for producing the same, and the light conversion adhesive film will be described in further detail with reference to specific examples.

[0127] Example 1

[0128] First, the organic light conversion agent is prepared according to the following procedure:

[0129] 10 g of 7-amino-4-methylcoumarin, 13 g of p-toluenesulfonyl chloride, and 9 g of pyridine are mixed with 60 mL of dimethylacetamide (DMAC) and heated at 80°C for 4 hours to convert into (HN-Ts)-methylcoumarin.

[0130] Then, 10 g of (HN-Ts)-methylcoumarin and 15 g of anhydrous K2CO3 are refluxed in 50 mL of dry acetone, and 4 g of bromobutane is added to introduce the R1 group to obtain (butyl-N-Ts)-methylcoumarin. This reaction occurs within 4 hours.

[0131] 10 g of (butyl-N-Ts)-methylcoumarin, 30 mL of acetic acid, and 10 mL of concentrated sulfuric acid are mixed and stirred at 120°C for 4 hours. After the reaction is completed, the reaction solution is poured into 400 mL of deionized water, and stirred and filtered to remove insoluble solids. The filtrate is neutralized to neutrality using sodium carbonate, and a large amount of precipitate is generated during the process. After being filtered and washed with deionized water twice, the obtained solid is dried in a vacuum oven at 60°C for 24 hours to obtain (butyl-N-H)-coumarin.

[0132] Finally, 2.5 g of (butyl-N-H)-coumarin was reacted with 1.80 g of allyl bromide and 4.97 g of anhydrous K2CO3 in dry 30 mL of DMAC at 60 °C for 24 h. After the reaction was completed, 7-(butyl-N-allyl)-4-methylcoumarin was obtained after filtration and distillation under reduced pressure.

[0133] The nuclear magnetic resonance results of the product are as follows:

[0134] 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (d, J = 7.6 Hz, 1H), 6.70 (dd, J = 7.5, 1.8 Hz, 1H), 6.65 (d, J = 1.9 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 5.86 (tt, J = 11.2, 5.5 Hz, 1H), 5.14 (dddt, J = 16.9, 11.4, 2.1, 1.0 Hz, 2H), 3.77 (dt, J = 5.5, 0.9 Hz, 2H), 3.25 (t, J = 6.5 Hz, 2H), 2.44 (d, J = 1.3 Hz, 3H), 1.54 (p, J = 6.7 Hz, 2H), 1.36 (dt, J = 14.2, 7.1 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H)).

[0135] (ii) Surface modification of the inorganic fluorescent powder to prepare a surface-modified inorganic light conversion agent, the specific steps are:

[0136] The nitride SrSi2O2N2:Eu 2+ For light conversion agent, SrSi2O2N2:Eu 2+ was dispersed uniformly by ultrasonicating in anhydrous ethanol, and then deionized water, ammonia, dodecyltrimethylsiloxane, and γ-methacryloyloxypropyltrimethoxysilane (mass ratio of 10:10:0.5:0.5) were sequentially added, and the mixture was stirred for 24 h. Among them, SrSi2O2N2:Eu 2+ The mass ratio of the silane coupling agent (the sum of dodecyltrimethylsiloxane and γ-methacryloyloxypropyltrimethoxysilane) to SrSi2O2N2:Eu was 1:0.01. After the reaction was completed, the stirring was stopped, and the turbid liquid was allowed to naturally settle. It was observed that the fluorescent material could almost completely settle to the bottom after the modification was successful, and the supernatant was discarded. The fluorescent material was washed with an appropriate amount of petroleum ether 4 times, and then was filtered and dried in a vacuum oven at 60 °C for 24 h. Finally, the surface-modified SrSi2O2N2:Eu 2+ The fluorescent powder is coated with a thin layer of silane coupling agent on the surface.

[0137] (iii) Hybridization

[0138] The obtained organic light-conversion agent 7-(butyl-N-allyl)-4-methyl coumarin and the obtained surface-modified inorganic light-conversion agent are mixed in a weight ratio of 1:1 to obtain an organic-inorganic hybrid light-conversion agent (also referred to as a composite light-conversion agent).

[0139] (4) Film formation

[0140] Finally, the composite light-conversion agent obtained in (3) (0.2 parts) is mixed with a base resin (EVA, 98 parts), a crosslinking agent (t-butyl peroxy carbonate-2-ethylhexyl ester, 0.3 parts), a co-crosslinking agent (propoxylated glyceryl triacrylate, 0.5 parts), a light stabilizer (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.2 parts), a silane coupling agent (γ-aminopropyl triethoxysilane, 0.5 parts), an antioxidant (tetra[β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, 0.2 parts), and an anti-aging agent (2,6-di-t-butyl-p-cresol, 0.1 parts) at 30°C until they are uniformly dispersed. The stirred semi-finished product is left to stand for 5 h, and then is put into a device and extruded at 100°C by a screw, and is cast to cool to obtain a light-conversion film.

[0141] It should be noted that, in the following examples, in order to remove the influence of different components, the base resin, the crosslinking agent, the co-crosslinking agent, the silane coupling agent, the light stabilizer, the antioxidant, and the anti-aging agent all use the same additive components as in Example 1. However, for other components, the inventors have verified through a large number of experiments that they can also be applicable and have similar effects, and detailed descriptions thereof are omitted here and are not enumerated exhaustively.

[0142] Example 2

[0143] (1) First, an organic light-conversion agent is prepared, and the specific steps are as follows:

[0144] 10 g of 7-amino-4-methyl coumarin, 13 g of p-toluenesulfonyl chloride, and 9 g of pyridine and 60 mL of DMAC are heated at 80°C for 4 hours to convert into (HN-Ts)-methyl coumarin.

[0145] Then, 10 g of (HN-Ts)-methyl coumarin and 15 g of anhydrous K2CO3 are refluxed in dry 50 mL of acetone, 3.5 g of bromocyclopropane is added to introduce the R1 group, and (cyclopropyl-N-Ts)-methyl coumarin is obtained, and this reaction occurs within 4 hours.

[0146] 10 g (cyclopropyl-N-Ts)-methyl coumarin, 30 mL acetic acid and 10 mL concentrated sulfuric acid were mixed and stirred at 120°C for 4 hours. After the reaction was completed, the reaction solution was poured into 400 mL of deionized water, stirred and filtered to remove solid insoluble matter, and the filtrate was neutralized to neutral with sodium carbonate, during which a large amount of precipitate was produced. After filtration and washing with deionized water twice, the obtained solid was dried in a vacuum oven at 60°C for 24 h to obtain (cyclopropyl-N-H)-coumarin.

[0147] Finally, 2.5 g of (cyclopropyl-N-H)-coumarin was reacted with 2 g of alkenyl butyl bromide and 5 g of anhydrous K2CO3 in 30 ml of dry DMAC at 60°C for 24 hours. After the reaction was completed, 7-(cyclopropyl-N-alkenyl butyl)-4-methyl coumarin was obtained after filtration and distillation under reduced pressure.

[0148] The nuclear magnetic resonance data of the product are as follows:

[0149] 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (d, J = 7.6 Hz, 1H), 6.70 (dd, J = 7.5, 1.8 Hz, 1H), 6.65 (d, J = 1.9 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 5.86 (tt, J = 11.2, 5.5 Hz, 1H), 5.14 (dddt, J = 16.9, 11.4, 2.1, 1.0 Hz, 2H), 3.77 (dt, J = 5.5, 0.9 Hz, 2H), 3.25 (t, J = 6.5 Hz, 2H), 2.44 (d, J = 1.3 Hz, 3H), 1.54 (p, J = 6.7 Hz, 2H), 1.36 (dt, J = 14.2, 7.1 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H).

[0150] (ii) Surface modification of inorganic fluorescent powder to prepare surface-modified inorganic light conversion agent, the specific steps are as follows:

[0151] Select nitride SrSi2O2N2:Eu 2+ As a light conversion agent, the fluorescent material SrSi2O2N2:Eu 2+ was dispersed uniformly by ultrasonicating in anhydrous ethanol, and then deionized water, ammonia, hexadecyl trimethyl siloxane and 3-(methacryloyloxy) propyl trimethoxysilane (mass ratio of 10:10:0.5:0.5) were sequentially added, and the mixture was stirred for 24 h. Among them, SrSi2O2N2:Eu 2+The mass ratio of silane coupling agent (the sum of hexadecyl trimethyl siloxane and 3-(methacryloyloxy)propyl trimethoxysilane) to the phosphor is 1:0.05. After the reaction is completed, the stirring is turned off, and the phosphor is allowed to settle naturally. It is observed that the phosphor modified successfully can almost completely settle to the bottom after the supernatant is poured off. The phosphor is washed with an appropriate amount of petroleum ether 4 times, and then is transferred to a vacuum oven at 60°C for drying for 24 hours. The surface-modified SrSi2O2N2:Eu 2+ The phosphor is coated with a thin layer of silane coupling agent on the surface.

[0152] (Three) hybridization

[0153] The organic light-conversion agent obtained in (One) and the surface-modified inorganic light-conversion agent obtained in (Two) are mixed in a weight ratio of 3:2 to obtain a composite light-conversion agent.

[0154] (Four) film formation

[0155] The composite light-conversion agent obtained by the hybridization is mixed with a base resin (98 parts), a crosslinking agent (0.3 parts), a silane coupling agent (0.6 parts), a co-crosslinking agent (0.5 parts), a light stabilizer (0.1 parts), an antioxidant (0.2 parts), and an anti-aging agent (0.2 parts) at 40°C to obtain a homogeneous mixture. The homogeneous mixture is placed in a device and is extruded by a screw at 100°C to obtain a light-conversion film.

[0156] Example 3:

[0157] (One) First, an organic light-conversion agent is prepared according to the following steps:

[0158] 10g of 7-amino-4-methylcoumarin, 13g of p-toluenesulfonyl chloride, and 9g of pyridine are added to 60mL of DMAC, and the mixture is heated at 80°C for 4 hours to obtain (HN-Ts)-methylcoumarin.

[0159] Then, 10g of (HN-Ts)-methylcoumarin and 15g of anhydrous K2CO3 are refluxed in 50mL of dry acetone, and 3.5g of bromo-epoxypropane is added to introduce the R1 group to obtain (epoxypropyl-N-Ts)-methylcoumarin. The reaction is completed within 4 hours.

[0160] 10 g (epoxypropyl-N-Ts)-methylcoumarin, 30 mL acetic acid and 10 mL concentrated sulfuric acid were mixed and stirred at 120°C for 4 hours. After the reaction was completed, the reaction solution was poured into 400 mL of deionized water, stirred and filtered to remove the solid insoluble matter, and the filtrate was neutralized to neutral with sodium carbonate, during which a large amount of precipitate was generated. After filtration and washing with deionized water twice, the obtained solid was dried in a vacuum oven at 60°C for 24 h to obtain (epoxypropyl-N-H)-coumarin.

[0161] Finally, 2.5 g of (epoxypropyl-N-H)-coumarin was reacted with 2.0 g of alkenylbutyl bromide and 5 g of anhydrous K2CO3 in 30 ml of dry DMAC at 60°C for 24 hours. After the reaction was completed, 7-(epoxypropyl-N-alkenylbutyl)-4-methylcoumarin was obtained in good yield after filtration and distillation under reduced pressure.

[0162] The nuclear magnetic resonance data of the product are as follows:

[0163] 1 H NMR (500 MHz, Chloroform-d) δ 7.49 (d, J = 7.8 Hz, 1H), 6.70 (dd, J = 7.9, 1.8 Hz, 1H), 6.66 (d, J = 1.9 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 5.71 (tt, J = 11.1, 6.6 Hz, 1H), 5.00 (dddt, J = 19.8, 11.2, 2.2, 1.0 Hz, 2H), 4.69 (t, J = 2.5 Hz, 1H), 3.74 - 3.61 (m, 2H), 3.55 (dt, J = 12.4, 6.1 Hz, 1H), 3.41 (dd, J = 12.4, 2.5 Hz, 1H), 2.44 (d, J = 1.3 Hz, 3H), 2.28 - 2.13 (m, 2H).

[0164] (ii) Surface modification of inorganic fluorescent powder to prepare surface-modified inorganic light conversion agent, the specific steps are as follows:

[0165] Select nitride SrSi2O2N2:Eu 2+ As a light conversion agent, the fluorescent material SrSi2O2N2:Eu 2+ was dispersed uniformly by ultrasonicating in anhydrous ethanol, and then deionized water, ammonia water and 3-(methacryloyloxy)propyltrimethoxysilane (mass ratio of 10:10:2) were added in sequence, and stirred for 24 h. Among them, SrSi2O2N2:Eu 2+ The mass ratio of SrSi2O2N2:Eu and silane coupling agent (3-(methacryloyloxy)propyltrimethoxysilane) is 1:0.05.

[0166] After the reaction is completed, the stirring is turned off, and the turbid solution is allowed to settle naturally. The fluorescent material is observed to have settled almost completely to the bottom after the modification is successful, and the supernatant is discarded. The fluorescent material is washed with an appropriate amount of petroleum ether 4 times, and then is filtered under suction and is transferred to a vacuum oven at 60°C for drying for 24 hours. The surface-modified SrSi2O2N2:Eu is obtained finally. 2+ The fluorescent powder is coated with a thin layer of silane coupling agent on the surface.

[0167] (Three) Hybridization

[0168] The organic light-conversion agent obtained in (One) and the surface-modified inorganic light-conversion agent obtained in (Two) are mixed in a weight ratio of 2:3 to obtain a composite light-conversion agent.

[0169] (Four) Film formation

[0170] Then, the composite light-conversion agent obtained in (Three) (0.5 parts) is mixed uniformly with a base resin (97 parts), a crosslinking agent (0.3 parts), a silane coupling agent (0.7 parts), a co-crosslinking agent (0.7 parts), a light stabilizer (0.3 parts), an antioxidant (0.2 parts), and an anti-aging agent (0.3 parts) at a temperature of 50°C until they are uniformly dispersed. The stirred semi-finished product is allowed to stand for 10 hours, and then is placed in a device and is extruded through a screw at a temperature of 100°C, and is cast to cool to obtain a light-conversion film.

[0171] Example 4:

[0172] (One) First, an organic light-conversion agent is prepared according to the following steps:

[0173] 10 g of 7-amino-4-methylcoumarin, 13 g of p-toluenesulfonyl chloride, and 9 g of pyridine are mixed with 60 mL of DMAC, and the mixture is heated at 80°C for 4 hours to convert the (HN-Ts)-methylcoumarin.

[0174] Then, 10 g of (HN-Ts)-methylcoumarin and 15 g of anhydrous K2CO3 are refluxed in 50 mL of dry acetone, and 3.8 g of bromopentane is added to introduce the R1 group to obtain (pentyl-N-Ts)-methylcoumarin. This reaction occurs within 4 hours.

[0175] 10 g of (pentyl-N-Ts)-methylcoumarin, 30 mL of acetic acid, and 10 mL of concentrated sulfuric acid are mixed, and the mixture is stirred at 120°C for 4 hours. After the reaction is completed, the reaction solution is poured into 400 mL of deionized water, and the mixture is stirred and filtered to remove the insoluble solid. The filtrate is neutralized to neutral with sodium carbonate, and a large amount of precipitate is generated during the neutralization. After being filtered and washed with deionized water twice, the obtained solid is dried in a vacuum oven at 60°C for 24 hours to obtain (pentyl-N-H)-coumarin.

[0176] Finally, 2.5 g of (pentyl-N-H)-coumarin was reacted with 1.85 g of allyl bromide and 5 g of anhydrous K2CO3 in 30 ml of dry DMAC at 60°C for 24 hours. After the reaction, the product was obtained in good yield after filtration and distillation under reduced pressure.

[0177] The nuclear magnetic resonance data of the product are as follows:

[0178] 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (d, J = 7.6 Hz, 1H), 6.70 (dd, J = 7.5, 1.8 Hz, 1H), 6.65 (d, J = 1.9 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 5.86 (tt, J = 11.2, 5.5 Hz, 1H), 5.14 (dddt, J = 16.8, 11.4, 2.1, 1.0 Hz, 2H), 3.77 (dt, J = 5.5, 0.9 Hz, 2H), 3.24 (t, J = 5.9 Hz, 2H), 2.44 (d, J = 1.3 Hz, 3H), 1.65 (tt, J = 7.4, 5.8 Hz, 2H), 1.39 - 1.27 (m, 4H), 0.93 - 0.84 (m, 3H).

[0179] (ii) Surface modification of the inorganic fluorescent powder to prepare a surface-modified inorganic light conversion agent, the specific steps are:

[0180] The nitride CaAlSiN3:Eu 2+ is selected as the light conversion agent. 2+ It is uniformly dispersed by ultrasonic treatment in anhydrous ethanol, and then deionized water, ammonia water, γ-aminopropyl triethoxysilane and 3-(methacryloyloxy) propyl trimethoxysilane (mass ratio of 10:10:1:1) are sequentially added, and the mixture is stirred for 24 h. Among them, CaAlSiN3:Eu 2+ The mass ratio of CaAlSiN3:Eu

[0181] After the reaction is completed, the stirring is stopped, and the turbid liquid is allowed to settle naturally. It can be observed that the fluorescent material is almost completely settled at the bottom after the surface modification is successful, and the supernatant is discarded. The fluorescent material is washed with an appropriate amount of petroleum ether 4 times, and then is filtered and dried in a vacuum oven at 60°C for 24 h. Finally, the surface-modified commercial CaAlSiN3:Eu 2+ The fluorescent powder is coated with a thin layer of silane coupling agent on the surface.

[0182] (iii) Hybridization

[0183] The obtained organic light conversion agent 7-(pentyl-N-allyl)-4-methyl coumarin and the obtained surface modified inorganic light conversion agent were hybridized in a weight ratio of 1:1 to obtain a composite light conversion agent.

[0184] (4) Film formation

[0185] The composite light conversion agent (0.8 parts) was mixed with a base resin (96 parts), a crosslinking agent (0.5 parts), a co-crosslinking agent (0.8 parts), a silane coupling agent (0.7 parts), a light stabilizer (0.5 parts), and an antioxidant (0.5 parts), an anti-aging agent (0.2 parts) to obtain a homogeneous mixture, which was stirred at 20°C until uniformly dispersed. The stirred semi-finished product was left to stand for 30 h, and then was put into a device, and was extruded by a screw at 100°C, and was cast to cool to obtain a light conversion film.

[0186] Example 5

[0187] (1) First, an organic light conversion agent was prepared according to the following specific steps:

[0188] 10 g of 7-amino-4-methyl coumarin, 13 g of p-toluenesulfonyl chloride, and 9 g of pyridine were mixed with 60 mL of DMAC, and were heated at 80°C for 4 h to convert into (HN-Ts)-methyl coumarin.

[0189] Then, 10 g of (HN-Ts)-methyl coumarin and 15 g of anhydrous K2CO3 were refluxed in dry 50 mL of acetone, 5 g of iodododecane was added to introduce R1 group to obtain (dodecyl-N-Ts)-methyl coumarin, and the reaction was completed within 4 h.

[0190] 10 g of (dodecyl-N-Ts)-methyl coumarin, 30 mL of acetic acid, and 10 mL of concentrated sulfuric acid were mixed, and were stirred at 120°C for 4 h. After the reaction was completed, the reaction solution was poured into 400 mL of deionized water, and was stirred and filtered to remove solid insoluble matter. The filtrate was neutralized to neutral with sodium carbonate, and a large amount of precipitate was generated during the neutralization. After filtration and washing with deionized water twice, the obtained solid was dried in a vacuum oven at 60°C for 24 h to obtain (dodecyl-N-H)-coumarin.

[0191] Finally, 2.5 g of (dodecyl-N-H)-coumarin was reacted with 1.7 g of allyl bromide and 5 g of anhydrous K2CO3 in dry 30 mL of DMAC at 60°C for 24 h. After the reaction was completed, 7-(dodecyl-N-allyl)-4-methyl coumarin was obtained in a good yield after filtration and distillation under reduced pressure.

[0192] The nuclear magnetic resonance data of the product are as follows:

[0193] 1H NMR (500 MHz, Chloroform-d) δ 7.48 (d, J = 7.7 Hz, 1H), 6.69 (dd, J = 7.6, 1.9 Hz, 1H), 6.57 (d, J = 2.0 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 5.72 (tt, J = 16.5, 6.4 Hz, 1H), 5.00 (dddd, J = 19.8, 17.4, 2.2, 1.1 Hz, 2H), 3.41 (t, J = 6.0 Hz, 2H), 3.27 (t, J = 6.1 Hz, 2H), 2.44 (d, J = 1.3 Hz, 3H), 2.24 (qt, J = 6.1, 1.0 Hz, 2H), 1.67 - 1.59 (m, 1H), 1.37 - 1.24 (m, 17H), 0.94 - 0.85 (m, 3H).

[0194] (ii) surface modification of the inorganic fluorescent powder to prepare a surface-modified inorganic light conversion agent, the specific steps being:

[0195] The nitride CaAlSiN3:Eu 2+ is selected as the light conversion agent. 2+ The CaAlSiN3:Eu 2+ is dispersed uniformly in anhydrous ethanol by ultrasonic treatment, and then deionized water, ammonia, dodecyltrimethylsiloxane, and 3-(methacryloyloxy)propyltrimethoxysilane (mass ratio 10:10:2:0.5) are sequentially added, and the mixture is stirred for 24 h. The mass ratio of the CaAlSiN3:Eu 2+ to the silane coupling agent (the sum of the masses of dodecyltrimethylsiloxane and 3-(methacryloyloxy)propyltrimethoxysilane) is 1:0.1.

[0196] After the reaction is completed, the stirring is stopped, and the turbid solution is allowed to settle naturally. It is observed that the fluorescent material modified successfully can almost completely settle to the bottom after the modification, and the supernatant is discarded. The fluorescent material is washed with an appropriate amount of petroleum ether 4 times, and then is filtered and dried in a vacuum oven at 60°C for 24 h. Finally, the surface-modified CaAlSiN3:Eu 2+ The fluorescent powder is coated with a thin layer of silane coupling agent on the surface.

[0197] (iii) hybridization

[0198] The organic light conversion agent 7-(dodecyl-N-alkylbutyl)-4-methylcoumarin obtained in (i) and the surface-modified inorganic light conversion agent obtained in (ii) are mixed in a weight ratio of 2:1 to obtain a composite light conversion agent.

[0199] (iv) film formation

[0200] The composite light conversion agent (0.6 parts) is mixed with the base resin (96 parts), crosslinking agent (0.4 parts), co-crosslinking agent (0.8 parts), silane coupling agent (0.5 parts), light stabilizer (0.6 parts) and antioxidant (0.6 parts), anti-aging agent (0.5 parts) and stirred at 30°C until uniformly dispersed. The stirred semi-finished product is left to stand for 40 h, and then placed in the equipment, extruded at 100°C by means of a screw, and cast to cool to obtain the light conversion film.

[0201] Example 6:

[0202] (I) Preparation of the organic light conversion agent, the specific steps are as follows:

[0203] 10 g of 7-amino-4-methylcoumarin, 13 g of p-toluenesulfonyl chloride and 9 g of pyridine and 60 mL of dimethylacetamide (DMAC) are heated at 80°C for 4 hours to convert (HN-Ts)-methylcoumarin.

[0204] Then 10 g of (HN-Ts)-methylcoumarin and 15 g of anhydrous K2CO3 are refluxed in dry 50 mL of acetone, 4 g of bromobutane is added to introduce the R1 group to obtain (butyl-N-Ts)-methylcoumarin, and the reaction occurs within 4 hours.

[0205] 10 g of (butyl-N-Ts)-methylcoumarin, 30 mL of acetic acid and 10 mL of concentrated sulfuric acid are mixed and stirred at 120°C for 4 hours. After the reaction is completed, the reaction solution is poured into 400 mL of deionized water, stirred and filtered to remove solid insoluble matter, and the filtrate is neutralized to neutral with sodium carbonate, during which a large amount of precipitate is generated. After filtration, washing with deionized water twice, the obtained solid is dried in a vacuum oven at 60°C for 24 h to obtain (butyl-N-H)-coumarin.

[0206] 2.5 g of (butyl-N-H)-coumarin is reacted with 1.80 g of allyl bromide and 4.97 g of anhydrous K2CO3 in dry 30 mL of DMAC at 60°C for 24 hours. After the reaction is completed, 7-(butyl-N-allyl)-4-methylcoumarin is obtained after filtration and reduced pressure distillation.

[0207] 2 g of 7-(butyl-N-allyl)-4-methylcoumarin, 0.02 g of platinum acetylacetonate as catalyst, and 100 mL of triethoxysilane are subjected to hydrosilylation reaction, after stirring at 100°C for 24 h, the excess triethoxysilane is removed by reduced pressure distillation to obtain 7-(butyl-N-triethoxysilylpropyl)-4-methylcoumarin.

[0208] The nuclear magnetic resonance data of the product are as follows:

[0209] 1H NMR (500 MHz, Chloroform-d) δ 7.48 (d, J = 7.6 Hz, 1H), 6.64 (dd, J = 7.6, 1.9 Hz, 1H), 6.56 (d, J = 1.9 Hz, 1H), 6.09 (q, J = 1.4 Hz, 1H), 3.79 (q, J = 7.5 Hz, 6H), 3.45 (q, J = 7.3 Hz, 2H), 3.28 (t, J = 7.3 Hz, 2H), 2.44 (d, J = 1.3 Hz, 3H), 1.72 - 1.62 (m, 2H), 1.19 (dt, J = 24.0, 7.5 Hz, 12H), 0.77 (t, J = 9.5 Hz, 2H).

[0210] (ii) surface modification of the inorganic fluorescent powder to prepare a surface-modified inorganic light conversion agent, the specific steps being:

[0211] The nitride CaAlSiN3:Eu 2+ is selected as the light conversion agent, and the fluorescent material CaAlSiN3:Eu 2+ is dispersed in anhydrous ethanol under ultrasonication, and then deionized water, ammonia, isopropyl trimethoxysilane, and 3-(methacryloyloxy)propyl trimethoxysilane (mass ratio 10:10:1:2) are sequentially added, and the mixture is stirred for 24 h. The CaAlSiN3:Eu 2+ is mixed with the silane coupling agent (isopropyl trimethoxysilane and 3-(methacryloyloxy)propyl trimethoxysilane) at a mass ratio of 1:0.1.

[0212] After the reaction is completed, the stirring is stopped, and the turbid solution is allowed to naturally settle, and it can be observed that the fluorescent material modified successfully can almost completely settle at the bottom after the upper clear liquid is poured off; the fluorescent material is washed with an appropriate amount of petroleum ether 4 times, and then is filtered and transferred to a vacuum oven at 60°C for drying for 24 h. Finally, the surface-modified CaAlSiN3:Eu 2+ The fluorescent powder is coated with a thin layer of silane coupling agent on the surface.

[0213] (iii) hybridization

[0214] The organic light conversion agent 7-(butyl-N-triethoxysilylpropyl)-4-methylcoumarin obtained in (i) and the surface-modified inorganic light conversion agent obtained in (ii) are hybridized at a weight ratio of 2:1 to obtain a composite light conversion agent.

[0215] (iv) film formation

[0216] The composite light conversion agent (1 part) is mixed with the base resin (95 parts), crosslinking agent (0.8 parts), co-crosslinking agent (1 part), silane coupling agent (0.6 parts), light stabilizer (0.8 parts) and antioxidant (0.4 parts), anti-aging agent (0.6 parts) uniformly, and stirred at 40°C until uniformly dispersed. The stirred semi-finished product is left to stand for 40 h, and then put into the equipment, extruded by screw at 100°C, and cast cooled to obtain the light conversion film.

[0217] The light conversion adhesive film prepared in Examples 1-6 is subjected to various performance tests; at the same time, the surface-modified CaAlSiN3:Eu 2+ The fluorescent powder (i.e. the surface-modified inorganic light conversion agent obtained in (ii) of Example 6) is used as the light conversion agent (Comparative Example 1) and the pure organic light conversion agent, 7-(dodecyl-N-alkylbutyl)-4-methyl coumarin, is used as the light conversion agent (Comparative Example 2), which are respectively used to replace the composite light conversion agent in Example 6 to form a film, and the performance tests are carried out, and the specific test results are shown in Table 1.

[0218] Table 1 Performance test results

[0219]

[0220] The above results show that the organic-inorganic hybrid light conversion agent developed in the present application, when applied to the photovoltaic adhesive film, not only has excellent fluorescence quantum efficiency, can efficiently convert the absorbed 200-400 nm ultraviolet light into visible light, helps to improve the ultraviolet light conversion efficiency, increases the efficiency gain of the battery assembly, and prolongs the service life of the assembly. In addition, from Table 1, it can be seen that the fluorescence quantum efficiency of the light conversion adhesive film according to Examples 1-6 of the present application is significantly higher than that of Comparative Example 1 (i.e. using a pure inorganic light conversion agent), and has good stability (i.e. the fluorescence quantum efficiency does not decrease significantly after ultraviolet aging, while Comparative Example 2 (i.e. using a pure organic light conversion agent) has a more obvious decrease in fluorescence quantum efficiency in the later stage of ultraviolet aging), that is, the organic-inorganic hybrid light conversion agent according to the present application has the advantages of high luminous efficiency and high stability. The above is a preferred embodiment of the present application, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. An organic-inorganic hybrid light-converting agent, characterized in that, It is formed by chemical bonding between organic light-converting agents and surface-modified inorganic light-converting agents; The organic light-converting agent is 7-(R1-N-R2)-4-methylcoumarin, wherein at least one of the substituents in R1 and R2 contains a carbon-carbon double bond or a siloxane group. The surface-modified inorganic light-converting agent is an inorganic phosphor with a silane coupling agent layer coated on its surface.

2. The organic-inorganic hybrid light-converting agent according to claim 1, characterized in that, The substituent group containing the carbon-carbon double bond is an alkenyl group, an alkenyl group containing heteroatoms, a cycloalkenyl group, or a cycloalkenyl group containing heteroatoms. The substituent containing the siloxane group is the substituent obtained by hydrosilylation of the substituent containing the carbon-carbon double bond with a siloxysilane.

3. The organic-inorganic hybrid light-converting agent according to claim 2, characterized in that, The siloxysilane is trimethoxysilane, triethoxysilane, methyldimethoxysilane, or methyldiethoxysilane.

4. The organic-inorganic hybrid light-converting agent according to claim 1, characterized in that, The mass ratio of organic light-converting agent to surface-modified inorganic light-converting agent is 1:(0.5-2).

5. The organic-inorganic hybrid light-converting agent according to claim 1, characterized in that, The silane coupling agent layer is composed of at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane. or / and, The inorganic phosphor is at least one of nitride phosphor and oxide phosphor; or / and, The mass ratio of the silane coupling agent layer to the inorganic phosphor is (0.005-0.1):

1.

6. A method for preparing an organic-inorganic hybrid light-converting agent as described in any one of claims 1-5, characterized in that, Includes the following steps: Inorganic phosphors were dispersed in an organic solvent, and a silane coupling agent was added. The mixture was stirred for 5–36 h. The reaction product was then collected, washed, and dried to obtain a surface-modified inorganic phosphor. Organic light-converting agents are mixed with surface-modified inorganic light-converting agents to undergo a hybridization reaction, resulting in an organic-inorganic hybrid light-converting agent.

7. The method for preparing the organic-inorganic hybrid light-converting agent according to claim 6, characterized in that, Organic light-converting agents containing at least a carbon-carbon double bond or a siloxane group in their R2 substituents can be prepared using the following methods: A partial hydrogen atom in the amino group of 7-amino-4-methylcoumarin is replaced with toluenesulfonyl chloride to give (HN-Ts)-methylcoumarin; (HN-Ts)-methylcoumarin is reacted with a compound having an R1 substituent group introduced to generate (R1-N-Ts)-methylcoumarin; (R1-N-Ts)-methylcoumarin was detosulynized to give (R1-NH)-methylcoumarin; (R1-NH)-methylcoumarin is subjected to a substitution reaction with a compound containing an R2 substituent group containing a carbon-carbon double bond to generate 7-(R1-N-R2)-4-methylcoumarin, in which the R2 substituent group contains a carbon-carbon double bond. Alternatively, 7-(R1-N-R2)-4-methylcoumarin, whose R2 substituent contains a carbon-carbon double bond, can undergo a hydrosilylation reaction with a siloxysilane to generate 7-(R1-N-R2)-4-methylcoumarin, whose R2 substituent contains a siloxane group.

8. A light-converting adhesive film, characterized in that, By weight, it includes: Matrix resin, 70-99 parts; The organic-inorganic hybrid light-converting agent according to any one of claims 1-5, 0.01-5 parts; Crosslinking agent, 0.1-10 parts; Crosslinking agent, 0.1-10 parts; and Silane coupling agent, 0.1-10 parts.

9. The light-converting adhesive film according to claim 8, characterized in that, The light-converting film also includes other functional additives, 0.03-7 parts; The other functional additives include at least one of light stabilizers, antioxidants, and anti-aging agents.

10. The light-converting adhesive film according to claim 9, characterized in that, The matrix resin is one or more of EVA, POE, PVB, PMMA, and silicone resin; or / and, The crosslinking agent is at least one of one or more of the following: tert-butyl peroxycarbonate-2-ethylhexyl ester, 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-butyl peroxycarbonate isopropyl ester, 1,1-bis(tert-amylperoxy)cyclohexane, tert-amyl peroxycarbonate-2-ethylhexyl carbonate-tert-amyl peroxycarbonate, tert-amyl peroxycarbonate, and tert-butyl peroxy3,3,5-trimethylhexanoate. or / and, The co-crosslinking agent is at least one of glyceryl propoxylate, triallyl 1,3,5-cyanurate, trimethylolpropane triacrylate, triallyl isocyanurate, and polytriallyl isocyanurate. or / and, The silane coupling agent comprises one or more of the following: γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane. or / and, The light stabilizer is one or both of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and polysuccinate (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidinol). or / and, The antioxidant is selected from one or more of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; or / and, The anti-aging agent is selected from one or both of 2,6-di-tert-butyl-p-cresol and α-tocopherol.

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