Photoconversion adhesive film composition, photoconversion adhesive film, and photovoltaic module

Abstract

The present invention provides a photoconversion adhesive film composition, a photoconversion adhesive film, and a photovoltaic module. Calculated by weight percentage, the photoconversion adhesive film composition comprises 80% to 99.98% matrix resin, 0.01% to 10% photoconverter, and 0.01% to 10% auxiliary agents, wherein the photoconverter is a benzotriazole derivative, the general structural formula of the benzotriazole derivative is as shown in formula (I), where the R substituent is as shown in formula (a), and there is at least one R substituent at positions 4 and 7 of the benzotriazole derivative, and at least one R substituent at positions 5 and 6 of the benzotriazole derivative. The photoconversion adhesive film obtained from the above photoconversion adhesive film composition expands the absorption range of the material in the ultraviolet light region, thereby improving the solubility and photoconversion efficiency of the photoconversion adhesive film, and achieving a wider absorption range while ensuring the photostability of the photoconversion adhesive film. Therefore, the corresponding photoconversion adhesive film can provide better protection and gain effects to the battery module. [Formula 1] TIFF2026513525000070.tif28170 [2] TIFF2026513525000071.tif63170

Description

Cross-reference of related applications

[0001] This application is based on the Chinese application with CN application number 202310353493.6, filed on April 4, 2023, the Chinese application with CN application number 202311535255.3, filed on November 16, 2023, and the Chinese application with CN application number 202311712843.X, filed on December 13, 2022, and claims priority from all three, with the disclosures of the said CN applications again incorporated into this application as a whole. [Technical Field]

[0002] The present invention relates to the field of photoelectric technology, and more specifically to a photoconversion adhesive film composition, a photoconversion adhesive film, and a photovoltaic module. [Background technology]

[0003] In the first aspect, solar energy is an abundant, clean, and renewable resource, and therefore exploring new technologies to utilize solar energy more effectively has significant research significance and practical value. Currently, crystalline silicon batteries occupy a major position in the photovoltaic solar cell market, with mature production technology and stable applications. As market demands for battery module efficiency increase, crystalline silicon battery technology is also constantly innovating. Compared to most PERC and TOPCon batteries currently on the market, HJT batteries demonstrate a clear advantage in terms of photoelectric conversion efficiency and are expected to replace the former two and become the mainstream battery of the new generation. In recent years, the production capacity of HJT batteries has also been increasing.

[0004] However, HJT batteries are more sensitive to ultraviolet (UV) light in sunlight than PERC and TOPCon batteries. This means that HJT batteries cannot effectively utilize UV ​​light in sunlight, and the presence of UV light can cause irreversible damage to the battery, leading to a decrease in battery life and photoelectric conversion efficiency. Therefore, developing a packaging material-photoconversion adhesive film that can completely absorb UV light from the sun and convert it into visible light usable by the battery module will not only effectively prevent UV damage to the battery module, but will also provide a gain effect on the battery's photoelectric conversion efficiency.

[0005] The key to developing photoconverting adhesive films is developing an appropriate photoconverter. According to literature, organic photoconverters have advantages over inorganic, organic, and inorganic composite photoconverters in terms of price, structure, and compatibility with adhesive films. However, a drawback of organic photoconverters is their poor photostability. Currently, organic photoconverters based on benzotriazole derivatives have been reported in the literature, exhibiting relatively good photostability and making them a preferred material for developing high-performance photoconverting adhesive films.

[0006] However, currently reported benzotriazole-based organic photoconverters have only one absorption peak, at approximately 350 nm, resulting in a narrow effective absorption range and insufficient absorption of ultraviolet light below 400 nm. This means that the corresponding photoconverter adhesive film cannot effectively absorb ultraviolet light in sunlight, thereby failing to effectively protect the battery module.

[0007] In a second embodiment, wavelength conversion technology is a technique that utilizes the light absorption and conversion properties of a photoconverter by selecting an appropriate photoconverter and doping it into a polymer matrix, thereby enabling full utilization of the solar spectrum. This technology was initially applied only to agricultural film products. After 2000, with the development of the photovoltaic industry, scholars proposed applying this technology (wavelength conversion adhesive film) to photovoltaic devices. Theoretically, wavelength conversion adhesive film can be used to convert ultraviolet light, which is unusable by photovoltaic devices in sunlight, into usable visible light, thereby improving the photoelectric conversion efficiency of photovoltaic devices. However, the gain generated by this technology in actual applications of PERC and TOPCon batteries is limited.

[0008] However, with the recent advancements in HJT battery technology, the importance of wavelength conversion technology has once again become apparent. HJT batteries have higher theoretical efficiency than PERC and TOPCon batteries, and are therefore in a period of rapid development, and are expected to replace PERC batteries and become the mainstream in the market. However, HJT batteries have a lower utilization rate for ultraviolet light, and the modules are sensitive to ultraviolet light. Long-term exposure to ultraviolet light causes practical problems such as a decrease in the lifespan of the modules, and this is another problem that must be solved in order to make them a mature product. It is clear that selecting an appropriate wavelength conversion adhesive film is a more direct and economical solution than optimizing the photovoltaic module itself.

[0009] The core of wavelength conversion technology lies in selecting the appropriate photoconverter. Currently, the most widely reported wavelength conversion agents are organic photoconverters, inorganic photoconverters, and organic-inorganic composite photoconverters. However, considering indicators such as the photoconversion performance of the photoconverter (UV absorption, emission, and photoconversion efficiency), production costs, compatibility in adhesive films, dispersibility, and multifunctionality, organic photoconverters are the optimal choice. However, we face the fundamental requirement of maintaining a service life of at least 20 years for battery modules, and the drawbacks in terms of photostability of organic materials themselves are a significant factor threatening their reliability. For example, it has been reported that the efficiency of photovoltaic devices can be improved by preparing wavelength conversion adhesive films using the organic dye rhodamine as a photoconverter, but its photostability is very poor. In response to this, researchers have reported wavelength conversion adhesive films based on benzotriazole derivative organic photoconverters, which show significant improvement in photostability and excellent photoconversion performance. Therefore, benzotriazole derivative systems are ideal photoconverters for designing and developing highly reliable wavelength conversion adhesive films with strong photoconversion capabilities.

[0010] Conventional wavelength-based photoconverting adhesive films using benzotriazole derivatives as photoconverters exhibit good performance in terms of both photostability and photoconversion. However, in actual use scenarios of photovoltaic modules (exposed to sunlight), the packaging adhesive films covering the top and bottom surfaces are inevitably subjected to high temperatures (sometimes exceeding 90 degrees Celsius). At this time, a certain concentration difference of the photoconverter exists between the top adhesive film, which is doped with the photoconverter, and the bottom adhesive film, which does not. As a result, the photoconverter is prone to migrating downwards. This significantly reduces the absorption and conversion capacity of the top adhesive film for ultraviolet light, further affecting module efficiency and service life.

[0011] In the third aspect, solar energy is expected to become an alternative energy to replace conventional fossil fuels as clean energy with abundant resources and no need for transportation. Therefore, the development of solar energy collection and conversion technologies has gradually become a focus attracting attention from countries and society. A photovoltaic device can directly convert solar energy into electrical energy and is one of the most effective ways to utilize solar energy. So far, the demand for the quantity of photovoltaic devices worldwide has been continuously increasing.

[0012] Most photovoltaic devices can only effectively utilize the visible light and near-infrared light wavelength bands in sunlight, so the utilization efficiency for ultraviolet light (with a wavelength less than 400 nm) in sunlight is low. Moreover, the presence of ultraviolet light in sunlight further reduces the service life of photovoltaic devices, especially for heterojunction (HJT) cells which are expected to become the third-generation solar cells in place of PERC and TOPCon. The use of a wavelength conversion adhesive film can not only effectively and sufficiently absorb the ultraviolet light in sunlight and avoid damage to the service life of photovoltaic devices, but at the same time can convert the ultraviolet light into available visible light, thereby improving the photoelectric conversion efficiency of photovoltaic devices.

[0013] The technical core of the wavelength conversion film is to select an appropriate light conversion agent. Currently, the light conversion agents are mainly divided into inorganic light conversion agents and organic light conversion agents. Compared with inorganic light conversion agents, organic light conversion agents have the advantages of low price, many types, and easy performance control. Also, since the substrate material of the wavelength conversion film belongs to organic polymer materials, organic light conversion agents often show better dispersibility and compatibility with the substrate material and have a smaller impact on the light transmission performance of the wavelength conversion film. Ordinary organic light conversion agents are all some organic light-emitting small molecules with downward conversion. They can very well realize the absorption of ultraviolet light and convert it into visible light (generally blue light or sky blue light), and organic light conversion agents are often natural light conversion agent materials. However, most organic light conversion agents have relatively low stability, and the corresponding adhesive film usually has a high water vapor transmission rate, thereby greatly reducing the service life of photovoltaic modules.

Summary of the Invention

Problems to be Solved by the Invention

[0014] One of the main objects of the present invention is to provide a photo-conversion adhesive film composition, a photo-conversion adhesive film, and a photovoltaic module in order to solve the problems of low photoelectric conversion efficiency and short service life of traditional adhesive films in the prior art.

Means for Solving the Problems

[0015] In order to achieve the above object, according to one aspect of the present invention, a photo-conversion adhesive film composition is provided. Calculated by weight percentage, the photo-conversion adhesive film composition contains 80-99.98% of a matrix resin, 0.01-10% of a photo-conversion agent, and 0.01-10% of an auxiliary agent, provided that the photo-conversion agent is a benzotriazole derivative, and the general structural formula of the benzotriazole derivative is as follows.

Chemical formula

Chemical formula

[0016] Furthermore, the above R1 and R2 are each independently a substituted or unsubstituted C5-C10 C5~C alkyl group, at least one methylene group substituted with -COO- or -O- 10 Alkyl, substituted or unsubstituted C5-C 10 R1 and R2 are each independently selected from the alkenyl groups; preferably R1 and R2 are each independently selected from a group in which at least one methylene group of any of the groups pentyl, hexyl, heptyl, octyl, nonyl, or decyl is independently substituted with -COO- or -O-, or from the groups pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

[0017] Furthermore, the above benzotriazole derivatives are [ka] [ka] [ka] R1R3R4R5R6 is one or more selected from the following, where each R1R3R4R5R6 is independently a group in which at least one methylene group of any of the following groups is independently substituted with -COO- or -O-, or one selected from the following groups: pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group.

[0018] Furthermore, each of the above R1R3R4R5R6 is independently one or more selected from tert-butyl group, octyl group, nonyl group, hexenyl group, heptenyl group, octenyl group, ethyl butyrate group, propyl butyrate group, butyl butyrate group, dipropyl ether, dibutyl ether, and butylpentyl ether.

[0019] Furthermore, the above-mentioned benzotriazole derivatives include benzotriazole derivatives having the structures shown in (I) and (II), and preferably the molar ratio of benzotriazole derivatives having the structures shown in (I) and (II) is 1:0.01 to 0.5.

[0020] Furthermore, the above-mentioned auxiliary agent includes a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005 to 5%.

[0021] Furthermore, the above-mentioned auxiliary agent further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1 to 20%, more preferably 0.5 to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0022] Furthermore, the matrix resin is one or more selected from EVA, PVA, PMMA, POE, and silicone.

[0023] According to a further aspect of the present invention, a photoconverting adhesive film is provided which is prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the above-described photoconverting adhesive film composition.

[0024] According to a further aspect of the present invention, a photovoltaic module is provided, comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the photoconversion adhesive film described above.

[0025] Applying the technical solutions of this invention, the benzotriazole derivative of the present invention has a benzotriazole structure as its core, modified with R substituents around the benzene ring of benzotriazole, and forms an intramolecular DA interaction (charge transfer excited state) through the conjugation effect between the benzene rings, thereby constituting a light-emitting core. It is well known that the absorption of DA-type organic molecules includes not only the intrinsic absorption of the baseline in the molecule (generally within 300 nm) but also absorption due to charge transfer transitions from the donor group to the receptor group (between 300 and 400 nm).

[0026] In the benzotriazole derivative of this application, the donor group is the peripheral R substituent, and the receptor group is the benzotriazole located at the center of the benzotriazole derivative. The 4th and 7th positions of the benzotriazole derivative are symmetric, and the 5th and 6th positions are symmetric. In this application, both the 4(7) and 5(6) positions are modified with R substituents, and the transition levels of the 4(7) and 5(6) positions are different. As a result, the benzotriazole derivative undergoes a charge transfer transition and generates two different absorption peaks between 300 and 400 nm. This expands the absorption range of the material in the ultraviolet region, further improving its solubility and photoconversion efficiency. Moreover, it achieves a wider absorption range while ensuring the photostability of the photoconversion adhesive film. Therefore, the corresponding photoconversion adhesive film can provide better protection and gain effects to the battery module.

[0027] The second main objective of the present invention is to provide a wavelength conversion adhesive film composition, a wavelength conversion adhesive film, and a photovoltaic module in order to solve the problem in the prior art of low photoelectric conversion efficiency and short service life of photovoltaic modules due to the tendency for the photoconverter to migrate in wavelength conversion adhesive films using benzotriazole derivatives as photoconverters.

[0028] To achieve the above object, according to one aspect of the present invention, a wavelength-converting adhesive film composition is provided. Calculated by weight percentage, the wavelength-converting adhesive film composition includes 80 to 99.98% of a matrix resin, 0.01 to 10% of a light-converting agent, and 0.01 to 10% of an auxiliary agent. However, the light-converting agent is a benzotriazole-based derivative, and the general structural formula of the benzotriazole-based derivative is as follows. [Chemical formula] (Here, R1 and R are each independently a substituted or unsubstituted CH2=HC-R'-*, a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C1-C 20 alkoxy group, a substituted or unsubstituted C1-C 20 ester group, or a substituted or unsubstituted C1-C 20 amino group, and any one of the selections; R' is a direct bond or a C1-C 20 alkylene group; R2 and R3 are each independently H, a C1-C 20 hydrocarbon group, or a C3-C 20 hydrocarbon group in which at least one methylene group is substituted with -COO-. The light-converting agent has a maximum absorption wavelength between 300 and 400 nm and a maximum emission wavelength greater than 400 nm.)

[0029] Furthermore, any methylene group in R1 and R above is [Chemical formula] , -COO-, -O- are substituted with one of these; preferably R' is directly bonded or a C1-C8 alkylene group, and R1 and R are each independently selected from substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C1-C8 alkoxy groups, substituted or unsubstituted C1-C8 ester groups, or substituted or unsubstituted C1-C8 amino groups; preferably R1 and R are each independently a C1-C8 linear alkyl group, a C3-C8 branched alkyl group, C1- One selected from the C8 alkoxy groups; preferably R1 and R are independently a methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group, butyl group, butoxy group, pentyl group, pentyloxy group, hexyl group, hexyloxy group, heptyl group, heptyloxy group, octyl group, octyloxy group, vinyl group, allyl group, alkenylbutyl group, alkenylpentyl group, alkenylhexyl group, alkenylheptyl group, alkenyloctyl group, [ka] It is one of the following selected; further preferably, R1 and R are each independently an alkenyloctyl group, a heptyl group, [ka] It is one of the following that can be selected.

[0030] Furthermore, R1 and R are each substituents that are terminally sealed with an unsaturated substituted functional group, preferably the unsaturated substituted functional group is one selected from an olefin group, an acrylic acid group, or an acrylic acid ester group; preferably the unsaturated substituted functional group is a vinyl group; and / or, if R1 and R have substituents, the substituents are one or more selected from a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, or a nitro group.

[0031] Furthermore, R2 and R3 are independently H, C1~C 10 A hydrocarbon group, at least one methylene group substituted with -COO- C3~C10 One or more of the hydrocarbon groups selected from the following, preferably R2 and R3 are independently [ka] One or more of the following are selected, where "*" represents the bonding site to the respective benzene rings of R2 and R3.

[0032] Furthermore, the above benzotriazole derivatives are [ka] It is one or more of the following that can be selected.

[0033] Furthermore, the above-mentioned auxiliary agent includes a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005 to 5%.

[0034] Furthermore, the above-mentioned auxiliary agent further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1 to 20%, more preferably 0.5 to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0035] Furthermore, the matrix resin is one or more selected from EVA, PVA, PMMA, POE, and silicone.

[0036] According to another aspect of the present invention, a wavelength-converting adhesive film is provided, which is prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the aforementioned wavelength-converting adhesive film composition.

[0037] A further aspect of the present invention provides a photovoltaic module comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the wavelength conversion adhesive film described above.

[0038] Applying the technical solutions of this invention, the present invention optimizes the structure of the benzotriazole derivative. In addition to realizing the molecular photoconversion performance by connecting alkyl-substituted benzene rings to the 4th and 7th positions of the benzotriazole derivative, the multifunctionality of the photoconverter is realized by similarly connecting functional substituents to the 5th and / or 6th positions and the second N atom of the benzotriazole derivative. Among these, preferred R, R1R2, and R3 are advantageous in reinforcing the solubility of the photoconverter in the adhesive film, which not only suppresses migration and aggregation of the photoconverter in the adhesive film but also allows for the optimization of the absorption and emission spectra of the photoconverter as needed, thereby meeting the usage requirements of different manufacturers' modules in different scenes. Furthermore, even if there is a concentration difference of the photoconverter in the adhesive film, the mobility of the photoconverter decreases significantly at high temperatures.

[0039] The third main objective of the present invention is to provide a photoconversion adhesive film composition, a photoconversion adhesive film, and a photovoltaic module in order to solve the problems of conventional adhesive films having low photoelectric conversion efficiency, low stability, and short service life.

[0040] To achieve the above objective, according to one aspect of the present invention, a photoconversion adhesive film composition is provided, which, when calculated by weight percentage, comprises 80% to 99.98% of a matrix resin, 0.01% to 10% of a photoconverter, and 0.01% to 10% of an auxiliary agent, wherein the photoconverter is a benzotriazole compound, and the general structural formula of the benzotriazole compound is as follows. [ka] (R1 is a C3~C with at least one methylene group substituted with -COO-) 20 The alkyl group is such that R2 and R3 are independently H and C1-C 20The alkyl group, at least one methylene group substituted with -COO- C3~C 20 (One or more alkyl groups selected from the alkyl groups, and the auxiliary agent includes polyol compounds.)

[0041] Furthermore, when calculated by weight percentage, the above photoconversion adhesive film composition contains 98% to 99.98% matrix resin, 0.01% to 1% photoconverter, and 0.01% to 1% auxiliary agent, and more preferably the mass ratio of the photoconverter to the auxiliary agent is 1:2 to 500, and more preferably 1:2 to 50.

[0042] Furthermore, the mass of hydroxyl groups in the polyol compound is 0.1 to 20% of the mass of the polyol compound, preferably 0.5 to 10%, and preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0043] Furthermore, the above auxiliary agent further contains a polyester compound, preferably with a molecular weight of 500 to 80000, preferably with a mass ratio of 1:0.01 to 1 between the polyol compound and the polyester compound, preferably with a mass ratio of 1:0.1 to 0.5 between the polyol compound and the polyester compound, preferably with the polyester compound being an aliphatic polyester and / or an aromatic polyester, preferably with the aromatic polyester being polyethylene terephthalate, and preferably with the aliphatic polyester being C2 to C2 12 Aliphatic dibasic acids and C2-C 12 The alkyldiol is polymerized to obtain one or more polyester compounds selected from polyurethane; preferably, the aliphatic polyester is selected from one or more polyurethane, polybutylene succinate, polymethyl methacrylate, polyethylene glycol ester, and polyhydroxybutyrate.

[0044] Furthermore, the above R1 is a C3~C group in which at least one methylene group is substituted with -COO-. 10 It is an alkyl group, and preferably R1 is [ka] One or more of the following are selected, where "*" represents the binding site between the R1-excluded portion of the benzotriazole compound and R1.

[0045] Furthermore, R2 and R3 are independently H, C1~C 10 The alkyl group, at least one methylene group substituted with -COO- C3~C 10 One or more selected from the alkyl groups, preferably R2 and R3 are independently [ka] One or more selected from, where "*" represents the binding site between the portion of the benzotriazole compound excluding R2 and R2; more preferably, R2 is the same as R3, and preferably the benzotriazole compound is [ka] It is one or more of the following that can be selected.

[0046] Furthermore, the matrix resin is one or more selected from EVA, PVA, PMMA, POE, and silicone.

[0047] Furthermore, when the total mass of the matrix resin, photoconverter, and auxiliary agents is calculated as 100%, the photoconverter adhesive film composition further contains 0.01 to 1% crosslinking agent, preferably 0.01 to 0.5%.

[0048] According to another aspect of the present invention, a photoconverting adhesive film is provided which is prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the above-described photoconverting adhesive film composition.

[0049] According to yet another aspect of the present invention, a photovoltaic module is provided, comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the aforementioned photoconversion adhesive film.

[0050] By applying the technical solutions of the present invention, the ester group contained in R1 at the second N position of benzotriazole itself provides a first protective layer to the benzotriazole light-emitting core, and at the same time, the ester group having an oxygen atom can further form interactions with the matrix resin, such as hydrogen bonding, thereby reinforcing the compatibility between the photoconverter and the matrix resin and providing a second protective layer to the light-emitting core structure. The benzotriazole compound itself is limited by its relatively high rigidity, resulting in poor compatibility with the matrix resin. The alkyl main chain of the polyol compound additive is similar to the components of the matrix resin, and the hydroxyl functional group contained in the side chain of the polyol compound additive forms hydrogen bonds with the ester functional group of the photoconverter. Thus, through the dual action of similar compatibility and hydrogen bonding, the compatibility between the photoconverter and the matrix resin is reinforced, and at the same time, the matrix resin contributes to the protective effect on the photoconverter, providing a third protective layer to the light-emitting core structure. This multi-layer protective effect improves the stability of the photoconverter, optimizes the film formation effect, and further restricts the movement of the photoconverter within the matrix resin through actions such as hydrogen bonding, reducing energy loss in the molecular light emission process, reinforcing the molecular rigidity of the photoconverter, and ultimately achieving the objective of improving its light conversion efficiency. Therefore, the photoconverter adhesive film obtained using the photoconverter adhesive film composition of this invention possesses excellent photostability and high luminescence efficiency, and can effectively exert its effects over a long period of time, thereby improving the service life of the photovoltaic device. [Brief explanation of the drawing]

[0051] The drawings of the specification, which constitute part of this application, are used to provide a further understanding of the present invention, and the exemplary embodiments and descriptions thereof are used to interpret the present invention and do not unduly limit the present invention. The drawings are as follows.

[0052] [Figure 1] The absorption intensity diagrams of the photoconversion adhesive films provided in Example 1 and Comparative Example 1 of the present invention, respectively, are shown under different wavelengths. [Modes for carrying out the invention]

[0053] In cases where there is no conflict, the embodiments and features described herein can be combined with each other. The present invention will be described in detail below with reference to the drawings and by combining embodiments.

[0054] As analyzed in the first aspect of the background art of this application, conventional adhesive films in the prior art have problems such as low photoelectric conversion efficiency and short service life. To solve these problems, this application provides a photoelectric conversion adhesive film composition, a photoelectric conversion adhesive film, and a photovoltaic module.

[0055] In one typical embodiment of the present application, a photoconverting adhesive film composition is provided, calculated by weight percentage, comprising 80-99.98% of a matrix resin, 0.01-10% of a photoconverter, and 0.01-10% of an auxiliary agent, wherein the photoconverter is a benzotriazole derivative, and the general structural formula of the benzotriazole derivative is as follows. [ka] (Here, the R substituent is, [ka] The benzotriazole derivative has at least one R substituent at positions 4 and 7, and at least one R substituent at positions 5 and 6; R1 and R2 are independently H, substituted or unsubstituted C1-C 20 C3-C alkyl group, at least one methylene group substituted with -COO- or -O- 20 alkyl groups, substituted or unsubstituted C2-C 20The substituents are selected from the alkenyl groups, wherein the substituents at R1 and R2 are independently selected from one or more of the following: methyl, ethyl, propyl, butyl, trifluoromethyl, and nitro groups.

[0056] The benzotriazole derivative of the present invention has a benzotriazole structure as its core, and R substituents are added around the benzene ring of benzotriazole. The conjugation effect between the benzene rings forms intramolecular DA interactions (charge transfer excited states), constituting a light-emitting core. It is well known that the absorption of DA-type organic molecules includes not only the intrinsic absorption of the baseline in the molecule (generally within 300 nm) but also absorption due to charge transfer transitions from the donor group to the receptor group (between 300 and 400 nm).

[0057] In the benzotriazole derivative of this application, the donor group is the peripheral R substituent, and the receptor group is the benzotriazole located at the center of the benzotriazole derivative. The 4th and 7th positions of the benzotriazole derivative are symmetric, and the 5th and 6th positions are symmetric. In this application, both the 4(7) and 5(6) positions are modified with R substituents, and the transition levels of the 4(7) and 5(6) positions are different. As a result, the benzotriazole derivative undergoes a charge transfer transition and generates two different absorption peaks between 300 and 400 nm. This expands the absorption range of the material in the ultraviolet region, further improving its solubility and photoconversion efficiency. Moreover, it achieves a wider absorption range while ensuring the photostability of the photoconversion adhesive film. Therefore, the corresponding photoconversion adhesive film can provide better protection and gain effects to the battery module.

[0058] In some embodiments of this application, R1 and R2 are independently substituted or unsubstituted C5-C 10 C5~C alkyl group, at least one methylene group substituted with -COO- or -O- 10 Alkyl, substituted or unsubstituted C5-C 10R1 and R2 are each independently selected from the alkenyl groups; preferably R1 and R2 are each independently selected from a group in which at least one methylene group of any of the groups pentyl, hexyl, heptyl, octyl, nonyl, or decyl is independently substituted with -COO- or -O-, or from the groups pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

[0059] Preferably, R1 and R2 contribute by exhibiting a cooperative effect, for example, by improving the formation of interactions such as hydrogen bonding between R1 and the matrix resin, thereby reinforcing the compatibility between the photoconverter and the matrix resin and providing a more advantageous protective layer for the light-emitting core structure.

[0060] In order to improve the performance of the photoconverter, such as its photostability and photoconversion efficiency, the above-mentioned benzotriazole derivative is preferably: [ka] [ka] [ka] R1R3R4R5R6 is one or more selected from the following, where each R1R3R4R5R6 is independently a group in which at least one methylene group of any of the following groups is independently substituted with -COO- or -O-, or one selected from the following groups: pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group.

[0061] In one embodiment of the present application, R1R3R4R5R6 are each independently selected from one or more of the following: tert-butyl group, octyl group, nonyl group, hexenyl group, heptenyl group, octenyl group, ethyl butyrate group, propyl butyrate group, butyl butyrate group, dipropyl ether, dibutyl ether, and butylpentyl ether.

[0062] Preferably, the above types of benzotriazole derivatives further contribute to the cooperative relationship between them and the matrix resin and auxiliary agents, thereby being advantageous in improving the photoconversion efficiency of the photoconversion adhesive film.

[0063] In one embodiment of the present application, the benzotriazole derivative includes a benzotriazole derivative having the structures shown in (I) and (II), preferably with a molar ratio of benzotriazole derivatives having the structures shown in (I) and (II) being 1:0.01 to 0.5.

[0064] Because the benzotriazole derivatives with the structures shown in (I) and (II) have a relatively large number of R substituents, the degree of twisting of the benzotriazole derivative molecule itself is large, and the relatively large number of R substituents generate more electron transitions. Particularly preferable is to use the benzotriazole derivatives with the structures shown in (I) and (II) above as photoconverters, and to control the molar ratio of the two within the above range, thereby improving the cooperative effect between the benzotriazole derivatives and thereby improving the photoconversion efficiency of the photoconversion adhesive film.

[0065] In one embodiment of the present application, the auxiliary agent comprises a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005 to 5%.

[0066] The crosslinking agent is a molecule having multiple ethylenically unsaturated groups, which promotes crosslinking of polymers and can achieve a higher degree of crosslinking. The crosslinking agent in the above composition can be selected from those commonly used in this field, and preferably the crosslinking agent is tert-butylisopropyl percarbonate, 2,5-dimethyl-2,5-(bis-tert-butylperoxy)hexane, tert-butyloxy(2-ethylhexyl) carbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert- It is one or more selected from pentylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-amylperoxy 2-ethylhexyl carbonate, 2,5-dimethyl2,5-dimethyl2,5-dimethyl2,5-bis(benzoylperoxy)hexane, tert-amylperoxycarbonate, and tert-butyl(3,3,5-trimethylhexanoyl)peroxide.Preferably, auxiliary crosslinking agents include triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, and ditrimethylolpropane. It is one or more selected from tetraacrylate, ditrimethylolpropanetetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclodecanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate.

[0067] In one embodiment of the present application, the auxiliary agent further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1 to 20%, preferably 0.5 to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0068] Benzotriazole derivatives themselves are limited by their relatively high rigidity, resulting in poor compatibility with the matrix resin. The alkyl main chain of the polyol compound additive is similar to the components of the matrix resin, and the hydroxyl functional groups contained in the side chains of the polyol compound additive form hydrogen bonds with the ester functional groups of the photoconverter. Preferably, the hydroxyl group content in the polyol compound is within the above range, contributing to the improved compatibility between the photoconverter and the matrix resin. This further enhances the compatibility between the photoconverter and the matrix resin through the dual action of similar compatibility and hydrogen bonding.

[0069] In one embodiment of the present application, the auxiliary agent further comprises a thickening agent. The addition of a thickening agent can improve the adhesion between the adhesive film and the substrate. In preferred embodiments, the thickening agent includes, but is not limited to, one or more of the group consisting of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyloxypropyltrimethylsilane, and 3-aminopropyltrimethylsilane.

[0070] In some embodiments of the present application, the matrix resin is preferably one or more selected from EVA, PVA, PMMA, POE, and silicone, thereby exhibiting better cooperative action with components such as photoconverters, resulting in a high-performance photoconverting adhesive film. The matrix resin is inexpensive and contributes to cost reduction. Naturally, those skilled in the art can also use other matrix resins, which will not be described in detail here.

[0071] In one embodiment of the present application, when the total mass of the matrix resin, photoconverter, and auxiliary agent is calculated as 100%, the photoconverter adhesive film composition further contains 0.01 to 1% of a crosslinking agent, preferably 0.01 to 0.5%.

[0072] Preferably, the aforementioned photoconverter contributes to a cooperative effect with the crosslinking agent, thereby improving the crosslinking effect of the crosslinking agent and further improving the performance of the photoconverting adhesive film.

[0073] In another typical embodiment of the present application, a photoconverting adhesive film is provided, which is prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the aforementioned photoconverting adhesive film composition.

[0074] In some preferred embodiments of the present invention, after uniformly mixing the aforementioned photoconversion adhesive film compositions, a photoconversion adhesive film is prepared by a preparation process such as melt extrusion molding at 80 to 120°C. The resulting photoconversion adhesive film possesses excellent stability and high luminescence efficiency, and can effectively exert its effects over a long period of time, thereby improving the service life of the photovoltaic device.

[0075] In yet another typical embodiment of the present application, a photovoltaic module is provided, comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the photoconversion adhesive film described above.

[0076] The photovoltaic module including the above-described photoconversion adhesive film has excellent photoconversion efficiency and, naturally, may have more options depending on different needs and application scenarios. The photoconversion adhesive film of this invention is not limited to photovoltaic devices, agricultural films, architectural glass, and other fields.

[0077] The beneficial effects of this application will be further explained below with reference to the examples.

[0078] (Example 1) Calculated by weight parts, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of a benzotriazole compound (having the structure shown in (I)), 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.5 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate. The synthesis route of the benzotriazole derivative having the structure shown in (I) is as follows. [ka] After uniformly mixing the photoconversion adhesive film composition, the film was melt-extruded at 100°C to obtain a photoconversion adhesive film.

[0079] 1. Synthesis of M1 In a two-necked flask, o-phenylenediamine (3.67 g, 34 mmol) was heated and dissolved in 60 mL of glacial acetic acid. While stirring, an aqueous solution of sodium nitrite (2.76 g, 40 mmol) (30 mL) was slowly added dropwise. After the reaction mixture was clarified, stirring was continued for 2 hours to stop the reaction. The reaction mixture was frozen at -10°C to precipitate a white solid powder, which was then filtered and washed with water to obtain a white crude product. After recrystallization, 3 g of pure white crystalline powder was obtained, with a yield of 75%.

[0080] 2. Synthesis of M2 A mixture of M1 (2 g, 16.8 mmol), ethyl 4-bromobutanoate (3.92 g, 20 mmol), potassium carbonate (6.96 g, 50 mmol), and dimethylformamide (50 mL) was stirred under nitrogen and heated at 40°C for 2 days. The reaction mixture was poured into ice water and extracted with dichloromethane. The extracted organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a clear, oily crude product. Separation and purification were performed by column chromatography, using a petroleum ether / dichloromethane mixed solvent as the eluent, and finally 2.3 g of a pale yellow, oily pure product was obtained, with a yield of 60%.

[0081] 3. Synthesis of M3 M2 (2g, 8.6 mmol) was dissolved in 20 mL of nitric acid and heated. While stirring, liquid bromine (6.9 g, 43 mmol) was slowly added dropwise to the reaction system and stirred under reflux for 24 hours. The mixture was quenched with saturated sodium bisulfite aqueous solution to precipitate a solid, which was washed with water and filtered to obtain a grayish-white powdery crude product. This was recrystallized with dichloromethane to obtain 3.3 g of white solid powder, with a yield of 70%.

[0082] 4. Synthesis of M4 1,4-Benzenediboronic acid (2 g, 12 mmol), potassium carbonate (6.6 g, 48 mmol), and tetrakistriphenylphosphine palladium (0.4 g, 0.36 mmol) were mixed in a two-necked flask and purged with nitrogen gas. Ethyl 4-bromobutanoate (2.3 g, 12 mmol), 18 mL of toluene, and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. Separation and purification were performed by column chromatography, and ethyl acetate / petroleum ether was used as the eluent to obtain 1.98 g of a white solid product with a yield of 70%.

[0083] 5. Synthesis of product (I) M4 (3.5g, 14.8 mmol), M3 (2g, 3.6 mmol), potassium carbonate (3.3g, 24 mmol), and tetrakistriphenylphosphine palladium (0.23g, 0.2 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. The mixture was separated and purified by column chromatography, with ethyl acetate / petroleum ether as the eluent, and finally 2.8 g of a rice-white solid product was obtained, with a yield of 80%.

[0084] (Example 2) Calculated by weight parts, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of a benzotriazole compound (having the structure shown in (II)), 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.5 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate. The synthesis route of the benzotriazole derivative having the structure shown in (II) is as follows. [ka] After uniformly mixing the photoconversion adhesive film composition, the film was melt-extruded at 100°C to obtain a photoconversion adhesive film.

[0085] 1. Synthesis of M1 This is the same as the synthesis of M1 in Example 1.

[0086] 2. Synthesis of M2 This is the same as the synthesis of M2 in Example 1.

[0087] 3. Synthesis of M3 M2 (2g, 8.6 mmol) was dissolved in 20 mL of hydrobromic acid and heated to 100°C. While stirring, liquid bromine (5.5 g, 34.4 mmol) was slowly added dropwise to the reaction system and refluxed at 120°C for 24 hours. The mixture was quenched with saturated sodium bisulfite aqueous solution to precipitate a solid, which was washed with water and filtered to obtain a grayish-white powdery crude product. This was recrystallized with dichloromethane to obtain 3 g of white solid powder, with a yield of 75%.

[0088] 4. Synthesis of M4 This is the same as the synthesis of M4 in Example 1.

[0089] 5. Synthesis of product (II) M4 (2g, 8.5 mmol), M3 (1.25g, 2.66 mmol), potassium carbonate (1.47g, 10.6 mmol), and tetrakistriphenylphosphine palladium (0.3g, 0.27 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. The mixture was separated and purified by column chromatography, with ethyl acetate / petroleum ether as the eluent, and finally 1.82 g of a rice-white solid product was obtained, with a yield of 85%.

[0090] (Example 3) The difference from Example 1 is that the photoconverter is a benzotriazole derivative with the structure shown in (IV), and its synthesis route is as follows. [ka] Finally, a photoconversion adhesive film was obtained.

[0091] 1. Synthesis of M1 In a two-necked flask, 3,5-dibromo-1,2-phenylenediamine (9 g, 34 mmol) was heated and dissolved in 80 mL of glacial acetic acid. While stirring, an aqueous solution of sodium nitrite (2.76 g, 40 mmol) (30 mL) was slowly added dropwise. After the reaction mixture was clarified, stirring was continued for 2 hours to stop the reaction. The reaction mixture was frozen at -10°C to precipitate a white solid powder, which was then filtered and washed with water to obtain a white crude product. After recrystallization, 6.6 g of white powder was obtained, with a yield of 70%.

[0092] 2. Synthesis of M2 A mixture of M1 (4.65 g, 16.8 mmol), ethyl 4-bromobutanoate (3.92 g, 20 mmol), potassium carbonate (6.96 g, 50 mmol), and dimethylformamide (80 mL) was stirred under nitrogen gas and heated at 40°C for 2 days. The reaction mixture was poured into ice water and extracted with dichloromethane. The extracted organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a clear, oily crude product. Separation and purification were performed by column chromatography, using a petroleum ether / dichloromethane mixed solvent as the eluent, and finally 3.9 g of a pale yellow, oily pure product was obtained, with a yield of 60%.

[0093] 3. Synthesis of product (IV) 4-tert-butylphenylboronic acid (2 g, 8.5 mmol), M2 (1.6 g, 4 mmol), potassium carbonate (3.3 g, 24 mmol), and tetrakistriphenylphosphine palladium (0.23 g, 0.2 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. The mixture was separated and purified by column chromatography, with ethyl acetate / petroleum ether as the eluent, and finally 1.75 g of white solid powder was obtained, with a yield of 88%.

[0094] (Example 4) The difference from Example 1 is that the photoconverter is a benzotriazole derivative having the structures shown in (I) and (II), and the molar ratio of the benzotriazole derivatives having the structures shown in (I) and (II) is 1:0.2, ultimately yielding a photoconverting adhesive film.

[0095] (Example 5) The difference from Example 1 is that the photoconverter is a benzotriazole derivative having the structures shown in (I) and (II), and the molar ratio of the benzotriazole derivatives having the structures shown in (I) and (II) is 1:0.5, ultimately yielding a photoconverting adhesive film.

[0096] (Example 6) The difference from Example 1 is that the photoconverter is a benzotriazole derivative having the structures shown in (I) and (II), and the molar ratio of the benzotriazole derivatives having the structures shown in (I) and (II) is 1:0.01, ultimately yielding a photoconverting adhesive film.

[0097] (Example 7) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 99.95 parts by weight of ethylene vinyl acetate, 0.01 parts by weight of a benzotriazole compound having the structure shown in (II), 0.02 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.02 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, ultimately yielding a photoconversion adhesive film.

[0098] (Example 8) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 80 parts by weight of ethylene vinyl acetate, 10 parts by weight of a benzotriazole compound having the structure shown in (II), 5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 5 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, ultimately yielding a photoconversion adhesive film.

[0099] (Example 9) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of a benzotriazole compound (having the structure shown in (I)), 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, 0.3 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, and 0.2 parts by weight of polyvinyl alcohol, with the mass of hydroxyl groups in the polyvinyl alcohol being 0.5% of the mass of polyvinyl alcohol, and a photoconversion adhesive film was finally obtained.

[0100] (Example 10) The difference from Example 9 is that the mass of hydroxyl groups in the polyvinyl alcohol is 10% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0101] (Example 11) The difference from Example 9 is that the mass of hydroxyl groups in the polyvinyl alcohol is 0.1% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0102] (Example 12) The difference from Example 9 is that the mass of hydroxyl groups in the polyvinyl alcohol is 20% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0103] (Example 13) The difference from Example 9 is that the polyol compound is polyethylene glycol, and ultimately a photoconvertible adhesive film was obtained.

[0104] (Example 14) The difference from Example 1 is that, when calculated by weight, the matrix resin is ethylene-1-octene, and a photoconversion adhesive film was ultimately obtained.

[0105] (Comparative Example 1) The difference from Example 1 is that the general structural formula of the benzotriazole compound is as follows. [ka] Finally, a photoconversion adhesive film was obtained.

[0106] (Comparative Example 2) The difference from Example 3 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 70 parts by weight of matrix resin, 15 parts by weight of a benzotriazole compound having the structure shown in (II), and 15 parts by weight of polyvinyl alcohol (molecular weight 1000, with the mass of hydroxyl groups in the polyol compound being 5% of the mass of polyvinyl alcohol), ultimately yielding a photoconversion adhesive film.

[0107] (Comparative Example 3) The coated photoconverting powder consists of a benzotriazole derivative organic photoconverter and a silica ALD coating layer. The photoconverter has a particle size D50 of 10 nanometers and a specific surface area of ​​2000 m². 2 The concentration is / g, the silica coating layer thickness is 1 nanometer, and the molecular formula of the organic photoconverter is as shown in formula B-1. [ka]

[0108] The above photoconversion powder was used in an EVA photovoltaic adhesive film. In addition to containing 100 parts EVA resin and 0.05 parts photoconversion powder, the adhesive film also contained 0.5 parts peroxide crosslinking agent, 0.1 parts auxiliary crosslinking agent, and 0.5 parts silane coupling agent. After laminating and crosslinking the adhesive film, the light transmittance in the 400-700 nanometer range was 91%. When this was applied to an HJT module, the initial power generation was improved by 1% compared to the same adhesive film without the photoconversion powder. The module's power generation decreased by 1.3% after moist heat aging and by 1.8% after ultraviolet aging.

[0109] (Comparative Example 4) The difference from Example 1 is that the molecular formula of the organic photoconverter is as shown in formula B-1. [ka] Finally, a photoconversion adhesive film was obtained.

[0110] Test method Light conversion efficiency: The absolute quantum efficiency will be tested using an integrating sphere at room temperature with a Horiba FL-3 spectrometer.

[0111] Aging test: The upper and lower surfaces of the photoconversion adhesive films obtained in Examples 1 to 14 and Comparative Examples 1 to 4 were laminated with a glass layer to obtain pre-pressurized modules, and UV300 aging tests were performed in UV aging boxes with multiple times the power (power 142W, temperature 70°C).

[0112] Yellowing Index: The yellowing index (ΔYI) of the pre-pressurized module before and after the aging test was measured according to the Chinese national standard GB 2409, "Test Method for Plastic Yellowing Index." The test results are shown in Table 1. [Table 1(1)]

[0113] As can be seen from the above description, the above embodiment of the present invention achieves the following technical effects.

[0114] The benzotriazole derivative of the present invention has a benzotriazole structure as its core, and R substituents are added around the benzene ring of benzotriazole. The conjugation effect between the benzene rings forms intramolecular DA interactions (charge transfer excited states), constituting a light-emitting core. It is well known that the absorption of DA-type organic molecules includes not only the intrinsic absorption of the groups in the molecule (generally within 300 nm) but also absorption due to charge transfer transitions from the donor group to the receptor group (between 300 and 400 nm).

[0115] In the benzotriazole derivative of this application, the donor group is the peripheral R substituent, and the receptor group is the benzotriazole located at the center of the benzotriazole derivative. The 4th and 7th positions of the benzotriazole derivative are symmetric, and the 5th and 6th positions are symmetric. In this application, both the 4(7) and 5(6) positions are modified with R substituents, and the transition levels of the 4(7) and 5(6) positions are different. As a result, the benzotriazole derivative undergoes a charge transfer transition and generates two different absorption peaks between 300 and 400 nm. This expands the absorption range of the material in the ultraviolet region, further improving its solubility and photoconversion efficiency. Moreover, it achieves a wider absorption range while ensuring the photostability of the photoconversion adhesive film. Therefore, the corresponding photoconversion adhesive film can provide better protection and gain effects to the battery module.

[0116] As analyzed in the second aspect of the background art of this application, in the prior art, there is a problem in that the photoelectric conversion efficiency of photovoltaic modules is low and the service life is short due to the tendency of the photoconverter to migrate in wavelength-based photoconverting adhesive films using benzotriazole derivatives as photoconverters. To solve this problem, this application provides a wavelength-based adhesive film composition, a wavelength-based adhesive film, and a photovoltaic module.

[0117] In one typical embodiment of the present application, a wavelength conversion adhesive film composition is provided, calculated by weight percentage, comprising 80-99.98% matrix resin, 0.01-10% photoconverter, and 0.01-10% auxiliary agent, wherein the photoconverter is a benzotriazole derivative, and the general structural formula of the benzotriazole derivative is as follows. [ka] (Here, R1 and R are independently substituted or unsubstituted CH2=HC-R'-* and substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C1-C 20 alkoxy group, substituted or unsubstituted C1-C 20 Ester group, substituted or unsubstituted C1-C 20 R' is one of the amino groups selected from the following, and R' is directly bonded or C1~C 20 The alkylene group is; R2 and R3 are independently H, C1-C 20 A hydrocarbon group, at least one methylene group substituted with -COO- C3~C 20 The photoconverter is one of the hydrocarbon groups selected from the following; the photoconverter has a maximum absorption wavelength between 300 and 400 nm and a maximum emission wavelength greater than 400 nm.

[0118] This invention optimizes the structure of a benzotriazole derivative. In addition to achieving the photoconversion performance of the molecule by connecting alkyl-substituted benzene rings to the 4th and 7th positions of the benzotriazole derivative, it also achieves multifunctionality of the photoconverter by similarly connecting functional substituents to the 5th and / or 6th positions and the second N atom of the benzotriazole derivative. Among these, preferred R, R1R2, and R3 are advantageous in reinforcing the solubility of the photoconverter in the adhesive film, which not only suppresses migration and aggregation of the photoconverter in the adhesive film but also allows for the optimization of the absorption and emission spectra of the photoconverter as needed, thereby meeting the usage requirements of different manufacturers' modules in different scenes. Furthermore, even if there is a concentration difference of the photoconverter in the adhesive film, the mobility of the photoconverter decreases significantly at high temperatures.

[0119] In some embodiments of the present application, either the methylene group in R1 and R is, [ka] , -COO-, -O- are substituted with one of these; preferably R' is directly bonded or a C1-C8 alkylene group, and R1 and R are each independently selected from substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C1-C8 alkoxy groups, substituted or unsubstituted C1-C8 ester groups, or substituted or unsubstituted C1-C8 amino groups; preferably R1 and R are each independently a C1-C8 linear alkyl group, a C3-C8 branched alkyl group, C1- One selected from the C8 alkoxy groups; preferably R1 and R are independently a methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group, butyl group, butoxy group, pentyl group, pentyloxy group, hexyl group, hexyloxy group, heptyl group, heptyloxy group, octyl group, octyloxy group, vinyl group, allyl group, alkenylbutyl group, alkenylpentyl group, alkenylhexyl group, alkenylheptyl group, alkenyloctyl group, [ka] It is one of the following selected; further preferably, R1 and R are each independently an alkenyloctyl group, a heptyl group, [ka] It is one of the following that can be selected.

[0120] Preferably, R1 and R contribute to improving the solubility of the photoconverter in the matrix resin of the adhesive film and are advantageous in reducing aggregation of the photoconverter.

[0121] In some embodiments of the present application, R1 and R are substituents that are terminally encapsulated with an unsaturated substituted functional group, preferably the unsaturated substituted functional group is one selected from an olefin group, an acrylic acid group, or an acrylic acid ester group; preferably the unsaturated substituted functional group is a vinyl group; and / or, if R1 and R have substituents, the substituents are one or more selected from a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, or a nitro group.

[0122] Preferably, when R1 and R are substituents whose ends are sealed with one or more unsaturated substituted functional groups, the unsaturated bond among them undergoes a crosslinking reaction with the matrix in the wavelength conversion adhesive film, thereby fixing the photoconverter molecule and suppressing aggregation and migration phenomena of the photoconverter molecule in the wavelength conversion adhesive film.

[0123] In some embodiments of this application, R2 and R3 are independently H, C1-C 10 A hydrocarbon group, at least one methylene group substituted with -COO- C3~C 10 One or more of the hydrocarbon groups selected from the following, preferably R2 and R3 are independently [ka] One or more of the following are selected, where "*" represents the bonding site to the respective benzene rings of R2 and R3.

[0124] Preferred substituents R2 and R3 contribute to improved compatibility between the photoconverter and the matrix resin in the wavelength conversion adhesive film, providing a more advantageous protective layer for the light-emitting core structure.

[0125] To further improve the performance of the photoconverter, such as its photostability and photoconversion efficiency, the above-mentioned benzotriazole derivative is preferably: [ka] One or more of the following are selected, however, preferably R2 and R3 are tert-butyl groups, which contribute to reducing the probability of molecular planarization and further effectively reduce any possible π-π quenching fluorescence.

[0126] In one embodiment of the present application, the auxiliary agent comprises a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005 to 5%.

[0127] The crosslinking agent is a molecule having multiple ethylenically unsaturated groups, which promotes crosslinking of polymers and can achieve a higher degree of crosslinking. The crosslinking agent in the above composition can be selected from those commonly used in this field, and preferably the crosslinking agent is tert-butylisopropyl percarbonate, 2,5-dimethyl-2,5-(bis-tert-butylperoxy)hexane, tert-butyloxy(2-ethylhexyl) carbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert- It is one or more selected from pentylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-amylperoxy 2-ethylhexyl carbonate, 2,5-dimethyl2,5-dimethyl2,5-dimethyl2,5-bis(benzoylperoxy)hexane, tert-amylperoxycarbonate, and tert-butyl(3,3,5-trimethylhexanoyl)peroxide.Preferably, auxiliary crosslinking agents include triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, and ditrimethylolpropane. It is one or more selected from tetraacrylate, ditrimethylolpropanetetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclodecanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate.

[0128] In one embodiment of the present application, the auxiliary agent further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1 to 20%, preferably 0.5 to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0129] Benzotriazole derivatives themselves are limited by their relatively high rigidity, resulting in poor compatibility with the matrix resin. The alkyl main chain of the polyol compound additive is similar to the components of the matrix resin, and the hydroxyl functional groups contained in the side chains of the polyol compound additive form hydrogen bonds with the ester functional groups of the photoconverter. Preferably, the hydroxyl group content in the polyol compound is within the above range, contributing to the improved compatibility between the photoconverter and the matrix resin. This further enhances the compatibility between the photoconverter and the matrix resin through the dual action of similar compatibility and hydrogen bonding.

[0130] In one embodiment of the present application, the auxiliary agent further comprises a thickening agent. The addition of a thickening agent can improve the adhesion between the adhesive film and the substrate. In preferred embodiments, the thickening agent includes, but is not limited to, one or more of the group consisting of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyloxypropyltrimethylsilane, and 3-aminopropyltrimethylsilane.

[0131] In some embodiments of the present application, the matrix resin is preferably one or more selected from EVA, PVA, PMMA, POE, and silicone, thereby exhibiting better cooperative action with components such as photoconverters, resulting in a high-performance photoconverting adhesive film. The matrix resin is inexpensive and contributes to cost reduction. Naturally, those skilled in the art can also use other matrix resins, which will not be described in detail here.

[0132] In one embodiment of the present application, when the total mass of the matrix resin, photoconverter, and auxiliary agent is calculated as 100%, the wavelength conversion adhesive film composition further contains 0.01 to 1% crosslinking agent, preferably 0.01 to 0.5%.

[0133] Preferably, the aforementioned photoconverter contributes to a cooperative effect with the crosslinking agent, thereby improving the crosslinking effect of the crosslinking agent and further improving the performance of the wavelength conversion adhesive film.

[0134] In another typical embodiment of the present application, a wavelength-converting adhesive film is provided, which is prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the aforementioned wavelength-converting adhesive film composition.

[0135] In some preferred embodiments of the present invention, after uniformly mixing the aforementioned wavelength conversion adhesive film compositions, a wavelength conversion adhesive film is prepared by a preparation process such as melt extrusion molding at 80 to 120°C. The resulting wavelength conversion adhesive film possesses excellent stability and high luminescence efficiency, and can effectively exert its effects over a long period of time, thereby improving the service life of the photovoltaic device.

[0136] In yet another typical embodiment of the present application, a photovoltaic module is provided, comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the wavelength conversion adhesive film described above.

[0137] The photovoltaic module incorporating the wavelength conversion adhesive film described herein has excellent photoconversion efficiency and, naturally, may have more options depending on different needs and application scenarios. The wavelength conversion adhesive film described herein is not limited to photovoltaic devices, agricultural films, architectural glass, and other fields.

[0138] The beneficial effects of this application will be further explained below with reference to the examples.

[0139] (Example 1) Calculated by weight parts, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.5 parts by weight of a benzotriazole compound (having the structure shown in (I)), 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.2 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate. The synthesis route of the benzotriazole derivative having the structure shown in (I) is as follows. [ka]

[0140] The synthesis route for Example 1 is as follows: [ka]

[0141] 1. Synthesis of M1 In a two-necked flask, o-phenylenediamine (3.67 g, 34 mmol) was heated and dissolved in 60 mL of glacial acetic acid. While stirring, an aqueous solution of sodium nitrite (2.76 g, 40 mmol) (30 mL) was slowly added dropwise. After the reaction mixture was clarified, stirring was continued for 2 hours to stop the reaction. The reaction mixture was frozen at -10°C to precipitate a white solid powder, which was then filtered and washed with water to obtain a white crude product. After recrystallization, 3 g of pure white crystalline powder was obtained, with a yield of 75%.

[0142] 2. Synthesis of M2 M1 (2g, 16.8 mmol) was dissolved in 20 mL of nitric acid and heated. While stirring, liquid bromine (13.5 g, 84 mmol) was slowly added dropwise to the reaction system and stirred under reflux for 24 hours. The mixture was quenched with saturated sodium bisulfite aqueous solution to precipitate a solid, which was washed with water and filtered to obtain a grayish-white powdery crude product. This was recrystallized with ethanol to obtain 4.7 g of white solid powder, with a yield of 65%.

[0143] 3. Synthesis of M3 A mixture of M2 (2g, 4.6 mmol), 8-bromo-1-octene (1.1g, 5.6 mmol), potassium carbonate (1.95g, 14 mmol), and dimethylformamide (20 mL) was stirred under nitrogen gas and heated at 40°C for 2 days. The reaction mixture was poured into ice water and extracted with dichloromethane. The extracted organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a clear, oily droplet crude product. Separation and purification were performed by column chromatography, using a petroleum ether / dichloromethane mixed solvent as the eluent, and finally 1.6 g of a pale yellow, oily pure product was obtained, with a yield of 64%.

[0144] 4. Synthesis of M4 M3 (2g, 3.6 mmol), 4-tert-butylphenylboronic acid (1.35g, 7.6 mmol), potassium carbonate (3.3g, 24 mmol), and tetrakistriphenylphosphine palladium (0.2g, 0.18 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, and then concentrated to obtain a pale yellow oily crude product.

[0145] 5. Synthesis of benzotriazole derivative 1 Crude M4 product, 7-alkenyloctylboronic acid (1.2 g, 7.6 mmol), potassium carbonate (3.3 g, 24 mmol), and tetrakistriphenylphosphine palladium (0.2 g, 0.18 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. Dichloromethane / petroleum ether was used as the eluent, and the mixture was separated by column chromatography to obtain 1.8 g of pure white solid powder, with a yield of 70%.

[0146] (Example 2) Calculated by weight parts, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.5 parts by weight of a benzotriazole compound (having the structure shown in (II)), 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.2 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate. The synthesis route of the benzotriazole derivative having the structure shown in (II) is as follows. [ka]

[0147] The synthesis route for Example 2 is as follows: [ka]

[0148] 1. Synthesis of M1 This is the same as the synthesis of M1 in Example 1.

[0149] 2. Synthesis of M2 M1 (2g, 16.8 mmol) was dissolved in 20 mL of nitric acid and heated. While stirring, liquid bromine (10.7 g, 67.2 mmol) was slowly added dropwise to the reaction system and stirred under reflux for 24 hours. The mixture was quenched with saturated sodium bisulfite aqueous solution to precipitate a solid, which was washed with water and filtered to obtain a grayish-white powdery crude product. This was recrystallized with ethanol to obtain 3.6 g of white solid powder, with a yield of 60%.

[0150] 3. Synthesis of M3 A mixture of M2 (2g, 5.6 mmol), 2-bromoethyl acrylate (1.2g, 6.7 mmol), potassium carbonate (2.3g, 16.8 mmol), and dimethylformamide (20 mL) was stirred under nitrogen gas and heated at 40°C for 2 days. The reaction mixture was poured into ice water and extracted with dichloromethane. The extracted organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a clear, oily droplet crude product. Separation and purification were performed by column chromatography, using a petroleum ether / dichloromethane mixed solvent as the eluent, and finally, 1.5 g of a pale yellow solid pure product was obtained, with a yield of 60%.

[0151] 4. Synthesis of M4 M3 (2g, 4.4 mmol), 4-tert-butylphenylboronic acid (1.65g, 9.3 mmol), potassium carbonate (3.3g, 24 mmol), and tetrakistriphenylphosphine palladium (0.25g, 0.22 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, and then concentrated to obtain a pale yellow oily crude product.

[0152] 5. Synthesis of Benzotriazole Derivative 2 Crude M4 product, 7-alkenyloctylboronic acid (0.83 g, 5.3 mmol), potassium carbonate (2.8 g, 20 mmol), and tetrakistriphenylphosphine palladium (0.13 g, 0.11 mmol) were mixed in a two-necked flask and purged with nitrogen gas. 15 mL of toluene and 10 mL of deionized water were added to the reaction system. The mixture was stirred for 24 hours and then heated under reflux. The mixture was quenched in ice water, washed with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated, and mixed with the sample. Dichloromethane / petroleum ether was used as the eluent, and the mixture was separated by column chromatography to obtain 1.95 g of pure white solid powder with a yield of 75%.

[0153] (Example 3) The difference from Example 1 is that, when calculated by weight parts, the wavelength conversion adhesive film composition contains 99.95 parts by weight of ethylene vinyl acetate, 0.01 parts by weight of a benzotriazole compound with the structure shown in Example 1, 0.02 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 0.02 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, ultimately yielding a wavelength conversion adhesive film.

[0154] (Example 4) The difference from Example 1 is that, when calculated by weight parts, the wavelength conversion adhesive film composition contains 80 parts by weight of ethylene vinyl acetate, 10 parts by weight of a benzotriazole compound with the structure shown in Example 1, 5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, and 5 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, ultimately yielding a wavelength conversion adhesive film.

[0155] (Example 5) The difference from Example 1 is that, when calculated by weight parts, the wavelength conversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of the benzotriazole compound from Example 2, 0.5 parts by weight of the crosslinking agent tert-butylisopropyl percarbonate, 0.3 parts by weight of the auxiliary crosslinking agent trimethylolpropanetetraacrylate, and 0.2 parts by weight of polyvinyl alcohol, with the mass of hydroxyl groups in the polyvinyl alcohol being 0.5% of the total polyvinyl alcohol mass, ultimately yielding a wavelength conversion adhesive film.

[0156] (Example 6) The difference from Example 5 is that the mass of hydroxyl groups in the polyvinyl alcohol is 10% of the mass of the polyvinyl alcohol, and a wavelength-converting adhesive film was ultimately obtained.

[0157] (Example 7) The difference from Example 5 is that the mass of hydroxyl groups in the polyvinyl alcohol is 0.1% of the total polyvinyl alcohol mass, and a wavelength-converting adhesive film was ultimately obtained.

[0158] (Example 8) The difference from Example 5 is that the mass of hydroxyl groups in the polyvinyl alcohol is 20% of the mass of the polyvinyl alcohol, and a wavelength-converting adhesive film was ultimately obtained.

[0159] (Example 9) The difference from Example 5 is that the polyol compound is polyethylene glycol, and ultimately a wavelength-converting adhesive film was obtained.

[0160] (Example 10) The difference from Example 1 is that, when calculated by weight, the matrix resin is ethylene-1-octene, and a wavelength-converting adhesive film was ultimately obtained.

[0161] (Comparative Example 1) The difference from Example 1 is that the general structural formula of the benzotriazole compound is as follows. [ka] Finally, a wavelength-converting adhesive film was obtained.

[0162] (Comparative Example 2) The difference from Example 1 is that, when calculated by weight parts, the wavelength conversion adhesive film composition contains 70 parts by weight of matrix resin, 15 parts by weight of a benzotriazole compound having the structure shown in Example 1, and 15 parts by weight of polyvinyl alcohol (molecular weight 1000, with the mass of hydroxyl groups in the polyol compound being 5% of the mass of polyvinyl alcohol), ultimately yielding a wavelength conversion adhesive film.

[0163] (Comparative Example 3) The coated photoconverting powder consists of a benzotriazole derivative organic photoconverter and a silica ALD coating layer. The photoconverter has a particle size D50 of 10 nanometers and a specific surface area of ​​2000 m². 2 The concentration is / g, the silica coating layer thickness is 1 nanometer, and the molecular formula of the organic photoconverter is as shown in formula B-1. [ka]

[0164] The above photoconversion powder was used in an EVA photovoltaic adhesive film. In addition to containing 100 parts EVA resin and 0.05 parts photoconversion powder, the adhesive film also contained 0.5 parts peroxide crosslinking agent, 0.1 parts auxiliary crosslinking agent, and 0.5 parts silane coupling agent. After laminating and crosslinking the adhesive film, the light transmittance in the 400-700 nanometer range was 91%. When this was applied to an HJT module, the initial power generation was improved by 1% compared to the same adhesive film without the photoconversion powder. The module's power generation decreased by 1.3% after moist heat aging and by 1.8% after ultraviolet aging.

[0165] (Comparative Example 4) The difference from Example 1 is that the molecular formula of the organic photoconverter is as shown in formula B-1. [ka] Finally, a wavelength-converting adhesive film was obtained.

[0166] Test method Light conversion efficiency: The absolute quantum efficiency will be tested using an integrating sphere at room temperature with a Horiba FL-3 spectrometer.

[0167] Aging Test: The upper and lower surfaces of the wavelength conversion adhesive films obtained in the above examples and comparative examples are laminated with a glass layer to obtain pre-pressurized modules, and a UV300 aging test is performed in a UV aging box with multiple times the power (142W power, 70°C temperature). Yellowing Index: The yellowing index (ΔYI) of the pre-pressurized modules before and after the aging test is measured according to the Chinese national standard GB 2409 "Test Method for Plastic Yellowing Index".

[0168] Mobility Test Method: A rapid aging mobility test was performed on the module ends. The front of the photovoltaic module was a wavelength-based light conversion film doped with a photoconverter, and the back of the module was a blank film without a photoconverter (only the photoconverter was variable). After the modules underwent UV300 aging experiments in an aging chamber, the adhesive film on the front of each module was peeled off and subjected to a heat immersion treatment in an organic solvent (methanol) (stirred at 60°C for 24 hours, then heated and immersed). HPLC analysis of the immersion solution was performed to obtain the content (A) of Example 1. The adhesive film on the front of an unaged module was peeled off, subjected to the same heat immersion treatment, and the immersion solution was subjected to HPLC analysis to obtain the content (B) of another Example 1. The mobility is A / B * 100%.

[0169] The results of the above tests are shown in Table 1. [Table 1(2)]

[0170] As can be seen from the above description, the above embodiment of the present invention achieves the following technical effects.

[0171] This invention optimizes the structure of a benzotriazole derivative. In addition to achieving the photoconversion performance of the molecule by connecting alkyl-substituted benzene rings to the 4th and 7th positions of the benzotriazole derivative, it also achieves multifunctionality of the photoconverter by similarly connecting functional substituents to the 5th and / or 6th positions and the second N atom of the benzotriazole derivative. Among these, preferred R, R1R2, and R3 are advantageous in reinforcing the solubility of the photoconverter in the adhesive film, which not only suppresses migration and aggregation of the photoconverter in the adhesive film but also allows for the optimization of the absorption and emission spectra of the photoconverter as needed, thereby meeting the usage requirements of different manufacturers' modules in different scenes. Furthermore, even if there is a concentration difference of the photoconverter in the adhesive film, the mobility of the photoconverter decreases significantly at high temperatures.

[0172] As analyzed in the third aspect of the background technology, conventional adhesive films in the prior art have problems such as low photoelectric conversion efficiency, low stability, and short service life. To solve these problems, the present invention provides a photoelectric conversion adhesive film composition, a photoelectric conversion adhesive film, and a photovoltaic module.

[0173] In one typical embodiment of the present application, a photoconverting adhesive film composition is provided, calculated by weight percentage, comprising 80% to 99.98% of a matrix resin, 0.01% to 10% of a photoconverter, and 0.01% to 10% of an auxiliary agent, wherein the photoconverter is a benzotriazole compound, and the general structural formula of the benzotriazole compound is as follows. [ka] (R1 is a C3~C with at least one methylene group substituted with -COO-) 20 The alkyl group is such that R2 and R3 are independently H and C1-C 20 The alkyl group, at least one methylene group substituted with -COO- C3~C 20 (One or more alkyl groups selected from the alkyl groups; the auxiliary agent includes a polyol compound.)

[0174] The ester group contained in R1 at the second N position of benzotriazole itself provides a first protective layer to the benzotriazole luminescent core. At the same time, the ester group having an oxygen atom can further form interactions with the matrix resin, such as hydrogen bonding, thereby reinforcing the compatibility between the photoconverter and the matrix resin and providing a second protective layer to the luminescent core structure. The benzotriazole compound itself is limited by its relatively high rigidity, resulting in poor compatibility with the matrix resin. The alkyl main chain of the polyol compound additive is similar to the components of the matrix resin, and the hydroxyl functional group contained in the side chain of the polyol compound additive forms hydrogen bonds with the ester functional group of the photoconverter. Thus, through the dual action of similar compatibility and hydrogen bonding, the compatibility between the photoconverter and the matrix resin is reinforced, and at the same time, the matrix resin contributes to the protective effect on the photoconverter, providing a third protective layer to the light-emitting core structure. This multi-layer protective effect improves the stability of the photoconverter, optimizes the film formation effect, and further restricts the movement of the photoconverter within the matrix resin through actions such as hydrogen bonding, reducing energy loss in the molecular light emission process, reinforcing the molecular rigidity of the photoconverter, and ultimately achieving the objective of improving its light conversion efficiency. Therefore, the photoconverter adhesive film obtained using the photoconverter adhesive film composition of this invention possesses excellent photostability and high luminescence efficiency, and can effectively exert its effects over a long period of time, thereby improving the service life of the photovoltaic device.

[0175] In one embodiment of the present application, when calculated by weight percentage, the above photoconversion adhesive film composition comprises 98% to 99.98% matrix resin, 0.01% to 1% photoconverter, and 0.01% to 1% auxiliary agent, and more preferably the mass ratio of the photoconverter to the auxiliary agent is 1:2 to 500, and more preferably 1:2 to 50.

[0176] The preferred content of the above photoconversion adhesive film composition contributes to the more effective performance of each component and improves the overall cooperative effect of each component. The above mass ratio of photoconverter and auxiliary agent is preferred, contributing to the full effectiveness of their cooperative effect and thereby reinforcing the compatibility between the photoconverter and the matrix resin.

[0177] In one embodiment of the present application, the mass of hydroxyl groups in the polyol compound is 0.1 to 20% of the mass of the polyol compound, preferably 0.5 to 10%, and preferably the molecular weight of the polyol compound is 500 to 80000, for example 500, 1000, 1500, 2000, 3000, 4000, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, or 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

[0178] If the amount of hydroxyl groups in the polyol compound is too high, it reduces the water vapor barrier properties of the photoconversion adhesive film. A polyol compound additive with a favorable amount of hydroxyl groups contributes to the formation of an appropriate amount of hydrogen bonds between the hydroxyl groups of the polyol compound and the ester groups of the photoconverter, thereby reinforcing the compatibility between the photoconverter and the matrix resin, further improving the stability of the photoconverter, optimizing the film formation effect, reinforcing the molecular rigidity of the photoconverter, and improving its photoconversion efficiency.

[0179] In one embodiment of the present application, the above-mentioned auxiliary agent further comprises a polyester compound, preferably having a molecular weight of 500 to 80000, preferably having a mass ratio of 1:0.01 to 1 between the polyol compound and the polyester compound, preferably having a mass ratio of 1:0.1 to 0.5 between the polyol compound and the polyester compound, preferably having an aliphatic polyester and / or an aromatic polyester, preferably having an aromatic polyester which is polyethylene terephthalate, and preferably having an aliphatic polyester which is C2 to C2 12 Aliphatic dibasic acids and C2-C 12The alkyldiol is polymerized to obtain one or more polyester compounds selected from polyurethane; preferably, the aliphatic polyester is selected from one or more polyurethane, polybutylene succinate, polymethyl methacrylate, polyethylene glycol ester, and polyhydroxybutyrate.

[0180] Hydrogen bonds are formed between the polyol compound and the photoconverter, and at the same time, the hydroxyl groups remaining in the polyol compound can form hydrogen bonds with oxygen atoms on the polyester compound. Furthermore, the alkyl main chain of the polyester compound is similar to the components of the matrix resin, indirectly reinforcing the compatibility between the photoconverter and the matrix resin. Simultaneously, the addition of the polyester compound reduces the amount of polyol compound added, effectively mitigating the problem of reduced water vapor barrier properties of the photoconverter adhesive film due to an excess of hydroxyl groups in the polyol compound. Preferably, the polyester compounds and their molecular weights are 500, 1000, 1500, 2000, 3000, 4000, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, or 80000, and the mass ratio of the polyol compounds contributes to improving the cooperative effect between the two, thereby giving the photoconverter and matrix resin excellent compatibility, while the photoconverter adhesive film has good water vapor barrier properties.

[0181] In some embodiments of the present application, preferably R1 is a C3-C3 group in which at least one methylene group is substituted with -COO-. 10 It is an alkyl group, and preferably R1 is [ka] One or more of the following are selected, where "*" represents the binding site between the R1-excluded portion of the benzotriazole compound and R1.

[0182] Preferably, the above types of ester groups contribute to better forming interactions such as hydrogen bonds with the matrix resin, thereby reinforcing the compatibility between the light conversion agent and the matrix resin, and providing a stronger protection effect for the light-emitting core structure.

[0183] In some embodiments of the present application, preferably, the above R2 and R3 are each independently H, C1-C 10 alkyl group, or any one or more selected from C3-C 10 alkyl groups in which at least one methylene group is substituted with -COO-, preferably R2 and R3 are each independently

Chemical formula

Chemical formula

[0184] Preferably, the above R2 and R3 substituents contribute to exerting a synergistic effect with R1, thereby more sufficiently protecting the light-emitting core.

[0185] Preferably, the above matrix resin is any one or more selected from EVA, PVA, PMMA, and POE, thereby better exerting a cooperative effect with components such as the light conversion agent, obtaining a light conversion adhesive film with excellent performance. The above matrix resins are inexpensive and contribute to cost reduction. Of course, those skilled in the art can also adopt other matrix resins, which will not be described in detail here.

[0186] In one embodiment of the present application, when calculating the total mass of the matrix resin, the light conversion agent and the auxiliary agent as 100%, the above light conversion adhesive film composition further contains 0.01 to 1% of a crosslinking agent, preferably 0.01 to 0.5%.

[0187] The preferred above-mentioned light conversion agent contributes to exerting a cooperative effect with the crosslinking agent, thereby improving the crosslinking effect of the crosslinking agent and further improving the performance of the light conversion adhesive film.

[0188] In another typical embodiment of the present application, there is provided a light conversion adhesive film prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is the above-mentioned light conversion adhesive film composition.

[0189] In some preferred embodiments of the present application, after uniformly mixing the above-mentioned light conversion adhesive film composition, a light conversion adhesive film is prepared by a preparation process such as melt extrusion molding at 80 to 120 °C. The obtained light conversion adhesive film has excellent stability and high luminous efficiency, and can effectively exert its function over a long period of time, thereby improving the service life of the photovoltaic device.

[0190] In yet another typical embodiment of the present application, there is provided a photovoltaic module including a light conversion adhesive film, wherein the light conversion adhesive film is the above-mentioned light conversion adhesive film.

[0191] The photovoltaic module including the above light conversion adhesive film of the present application has excellent photoelectric conversion efficiency. Naturally, it may have more choices according to different needs and application scenarios. The light conversion adhesive film of the present application is not limited to photovoltaic devices, agricultural films, architectural glass and other fields.

[0192] The beneficial effects of the present application will be further described below by referring to specific examples and comparative examples.

[0193] The benzotriazole compounds in Examples 1-4 below are known compounds in the prior art, and their synthesis methods should be referred to the relevant preparation methods at https: / / doi.org / 10.1016 / j.tet.2014.05.016.

[0194] (Example 1) Calculated by weight, the photoconversion adhesive film composition contains 98.8 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of a benzotriazole compound, and 1 part by weight of polyvinyl alcohol (with a molecular weight of 1000 and a hydroxyl group mass of 5% of the polyvinyl alcohol mass), provided that the general structural formula of the benzotriazole compound is as follows. [ka] After uniformly mixing the photoconversion adhesive film composition, the film was melt-extruded at 100°C to obtain a photoconversion adhesive film.

[0195] (Example 2) The difference from Example 1 is that the general structural formula of the benzotriazole compound is as follows. [ka] Finally, a photoconversion adhesive film was obtained.

[0196] (Example 3) The difference from Example 1 is that the general structural formula of the benzotriazole compound is as follows. [ka] Finally, a photoconversion adhesive film was obtained.

[0197] (Example 4) The difference from Example 1 is that the general structural formula of the benzotriazole compound is as follows. [ka] Finally, a light conversion adhesive film was obtained.

[0198] (Example 5) The difference from Example 1 is that, when calculated by parts by weight, the light conversion adhesive film composition contains 99.98 parts by weight of ethylene-vinyl acetate, 0.01 part by weight of a benzotriazole-based compound, and 0.01 part by weight of polyvinyl alcohol (having a molecular weight of 1000 and the mass of the hydroxyl group in the polyol-based compound being 5% of the mass of the polyvinyl alcohol), and finally a light conversion adhesive film was obtained.

[0199] (Example 6) The difference from Example 1 is that, when calculated by parts by weight, the light conversion adhesive film composition contains 80 parts by weight of ethylene-vinyl acetate, 10 parts by weight of a benzotriazole-based compound, and 10 parts by weight of polyvinyl alcohol (having a molecular weight of 1000 and the mass of the hydroxyl group in the polyol-based compound being 5% of the mass of the polyvinyl alcohol), and finally a light conversion adhesive film was obtained.

[0200] (Example 7) The difference from Example 1 is that, when calculated by parts by weight, the light conversion adhesive film composition contains 98 parts by weight of ethylene-vinyl acetate, 1 part by weight of a benzotriazole-based compound, and 1 part by weight of polyvinyl alcohol, and finally a light conversion adhesive film was obtained. [[ID=?]]

[0201] (Example 8) The difference from Example 1 is that, when calculated by parts by weight, the light conversion adhesive film composition contains 98 parts by weight of ethylene-vinyl acetate, 0.67 part by weight of a benzotriazole-based compound, and 1.33 parts by weight of polyvinyl alcohol, and finally a light conversion adhesive film was obtained.

[0202] (Example 9) The difference from Example 1 is that, when calculated by parts by weight, the light conversion adhesive film composition contains 98 parts by weight of ethylene-vinyl acetate, 0.039 part by weight of a benzotriazole-based compound, and 1.961 parts by weight of polyvinyl alcohol, and finally a light conversion adhesive film was obtained.

[0203] It seems there is a formatting issue or an unclear tag in the original text where an "?" is shown in the ID reference. Please correct that if possible for a more accurate translation.(Example 10) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 98 parts by weight of ethylene vinyl acetate, 0.08 parts by weight of a benzotriazole compound, and 1.92 parts by weight of polyvinyl alcohol, ultimately yielding a photoconversion adhesive film.

[0204] (Example 11) The difference from Example 1 is that the mass of hydroxyl groups in the polyvinyl alcohol is 0.5% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0205] (Example 12) The difference from Example 1 is that the mass of hydroxyl groups in the polyvinyl alcohol is 10% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0206] (Example 13) The difference from Example 1 is that the mass of hydroxyl groups in the polyvinyl alcohol is 0.1% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0207] (Example 14) The difference from Example 1 is that the mass of hydroxyl groups in the polyvinyl alcohol is 20% of the total polyvinyl alcohol mass, and a photoconversion adhesive film was ultimately obtained.

[0208] (Example 15) The difference from Example 1 is that the polyol compound is polyethylene glycol, and ultimately a photoconvertible adhesive film was obtained.

[0209] (Example 16) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 98.5 parts by weight of ethylene vinyl acetate, 1 part by weight of a benzotriazole compound, 0.25 parts by weight of polyvinyl alcohol (molecular weight 1000, with the mass of hydroxyl groups in the polyvinyl alcohol being 5% of the mass of the polyvinyl alcohol), and 0.25 parts by weight of polyethylene terephthalate (molecular weight 5000), ultimately yielding a photoconversion adhesive film.

[0210] (Example 17) The difference from Example 16 is that, when calculated by weight, the mass of ethylene-vinyl acetate remains unchanged, and the mass ratio of polyvinyl alcohol to polyethylene terephthalate is 1:0.01, ultimately yielding a photoconversion adhesive film.

[0211] (Example 18) The difference from Example 16 is that, when calculated by weight, the mass of ethylene-vinyl acetate remains unchanged, and the mass ratio of polyvinyl alcohol to polyethylene terephthalate is 1:0.5, ultimately yielding a photoconversion adhesive film.

[0212] (Example 19) The difference from Example 16 is that, when calculated by weight, the polyester compound is polyurethane, and ultimately a photoconversion adhesive film was obtained.

[0213] (Example 20) The difference from Example 16 is that, when calculated by weight, the matrix resin is ethylene-1-octene, and a photoconversion adhesive film was ultimately obtained.

[0214] (Example 21) The difference from Example 1 is that, when the total mass of the matrix resin, photoconverter, and auxiliary agents is calculated as 100%, the photoconverter adhesive film composition further contains 1% diisopropylbenzene hydroperoxide crosslinking agent, ultimately yielding a photoconverter adhesive film.

[0215] (Example 22) The difference from Example 1 is that, when the total mass of the matrix resin, photoconverter, and auxiliary agents is calculated as 100%, the photoconverter adhesive film composition further contains 0.01% diisopropylbenzene hydroperoxide crosslinking agent, ultimately yielding a photoconverter adhesive film.

[0216] (Example 23) The difference from Example 1 is that, when the total mass of the matrix resin, photoconverter, and auxiliary agents is calculated as 100%, the photoconverter adhesive film composition further contains 0.5% diisopropylbenzene hydroperoxide crosslinking agent, ultimately yielding a photoconverter adhesive film.

[0217] (Example 24) The difference from Example 21 is that the crosslinking agent is tert-butylperoxy-2-ethylhexyl carbonate crosslinking agent, and a photoconversion adhesive film was ultimately obtained.

[0218] (Comparative Example 1) The difference from Example 1 is that R1 is [ka] This is the point, and ultimately a photoconversion adhesive film was obtained.

[0219] (Comparative Example 2) The difference from Example 1 is that R1 is [ka] This is the point, and ultimately a photoconversion adhesive film was obtained.

[0220] (Comparative Example 3) The difference from Example 1 is that R1 is [ka] This is the point, and ultimately a photoconversion adhesive film was obtained.

[0221] (Comparative Example 4) The difference from Example 19 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 98.5 parts by weight of matrix resin, 1 part by weight of benzotriazole compound, and 0.5 parts by weight of polyurethane, ultimately yielding a photoconversion adhesive film.

[0222] (Comparative Example 5) The difference from Example 1 is that, when calculated by weight parts, the photoconversion adhesive film composition contains 70 parts by weight of matrix resin, 15 parts by weight of benzotriazole compound, and 15 parts by weight of polyvinyl alcohol (molecular weight 1000, with the mass of hydroxyl groups in the polyol compound being 5% of the mass of polyvinyl alcohol), ultimately yielding a photoconversion adhesive film.

[0223] Test method Light conversion efficiency: The absolute quantum efficiency will be tested using an integrating sphere at room temperature with a Horiba FL-3 spectrometer.

[0224] Aging test: The upper and lower surfaces of the photoconversion adhesive films obtained in Examples 1-24 and Comparative Examples 1-5 were laminated with a glass layer to obtain pre-pressurized modules, and UV300 aging tests were performed in UV aging boxes with multiple times the power (power 142W, temperature 70°C).

[0225] Yellowing Index: The yellowing index (ΔYI) of the pre-pressurized module before and after the aging test is measured according to the Chinese national standard GB 2409 "Test Method for Plastic Yellowing Index".

[0226] Water vapor transmission rate: The test method is based on standard GB / T 29848, "Ethylene-vinyl acetate copolymer (EVA) adhesive film for photovoltaic module packaging." The test results are shown in Table 1. [Table 1(3)]

[0227] Furthermore, the problem with both Comparative Example 1 and Comparative Example 5 is that their stability is extremely poor and their water vapor permeability is too high, which drastically reduces the service life of the photoconversion adhesive film and the corresponding photovoltaic module.

[0228] The problem with R1 being a carboxyl group in Comparative Example 2 is that the carboxyl group reacts with sodium silicate in the adjacent glass layer of the photoconversion adhesive film to produce sodium carboxylate, which affects film formation. At the same time, when used in a photoconversion adhesive film system, the carboxyl group causes the photoconversion adhesive film to corrode the welding ribbons, busbars, etc. of the photovoltaic module, and the stability of the carboxyl group is relatively poor.

[0229] The problem with R1 being a carbonyl group in Comparative Example 3 is that its stability is too poor and its water vapor permeability is too high, which drastically reduces the service life of the photoconversion adhesive film and the corresponding photovoltaic module.

[0230] By not adding the polyol compound to Comparative Example 4, its solubility decreases, and the light transmittance of the photoconversion adhesive film deteriorates.

[0231] As can be seen from the above description, the above embodiment of the present invention achieves the following technical effects.

[0232] The ester group contained in R1 at the second N position of benzotriazole itself provides a first protective layer to the benzotriazole luminescent core. At the same time, the ester group having an oxygen atom can further form interactions with the matrix resin, such as hydrogen bonding, thereby reinforcing the compatibility between the photoconverter and the matrix resin and providing a second protective layer to the luminescent core structure. The benzotriazole compound itself is limited by its relatively high rigidity, resulting in poor compatibility with the matrix resin. The alkyl main chain of the polyol compound additive is similar to the components of the matrix resin, and the hydroxyl functional group contained in the side chain of the polyol compound additive forms hydrogen bonds with the ester functional group of the photoconverter. Thus, through the dual action of similar compatibility and hydrogen bonding, the compatibility between the photoconverter and the matrix resin is reinforced, and at the same time, the matrix resin contributes to the protective effect on the photoconverter, providing a third protective layer to the light-emitting core structure. This multi-layer protective effect improves the stability of the photoconverter, optimizes the film formation effect, and further restricts the movement of the photoconverter within the matrix resin through actions such as hydrogen bonding, reducing energy loss in the molecular light emission process, reinforcing the molecular rigidity of the photoconverter, and ultimately achieving the objective of improving its light conversion efficiency. Therefore, the photoconverter adhesive film obtained using the photoconverter adhesive film composition of this invention possesses excellent photostability and high luminescence efficiency, and can effectively exert its effects over a long period of time, thereby improving the service life of the photovoltaic device.

[0233] The foregoing are merely preferred embodiments of the present invention and do not limit it; those skilled in the art will know that the present invention can be modified and altered in various ways. All modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photoconversion adhesive film composition, wherein, when calculated by weight percentage, the photoconversion adhesive film composition is 80% to 99.98% matrix resin, 0.01% to 10% of the photoconverter, It contains 0.01% to 10% of an auxiliary agent, The photoconverting adhesive film composition is characterized in that the photoconverting agent is a benzotriazole derivative, and the general structural formula of the benzotriazole derivative is as shown in formula I, formula II, or formula III. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 (however, In the above formula I, the R substituent is 【Chemistry 4】 The benzotriazole derivative has at least one R substituent at the 4th and 7th positions, and the benzotriazole derivative has at least one R substituent at the 5th and 6th positions, R １ and R ２ are each independently H, a substituted or unsubstituted C １ to C ２０ alkyl group, a C ３ to C ２０ alkyl group in which at least one methylene group is substituted with -COO- or -O-, a substituted or unsubstituted C ２ to C ２０ alkenyl group, and are each any one selected therefrom, provided that the substituents in the said R １ and the said R ２ are each independently any one or more selected from a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, and a nitro group. In the above formula II, R １ And R are independently substituted or unsubstituted CH ２ = HC-R'-*, substituted or unsubstituted C １ ~C ２０ alkyl, substituted or unsubstituted C １ ~C ２０ alkoxy group, substituted or unsubstituted C １ ~C ２０ Ester group, substituted or unsubstituted C １ ~C ２０ R' is one of the amino groups selected from the following, and R' is directly bonded or C １ ~C ２０ It is an alkylene group, R ２ and R ３ These are H and C, respectively, independently. １ ~C ２０ C in which the hydrocarbon group, at least one methylene group is substituted with -COO- ３ ~C ２０ It is one of the hydrocarbon groups selected from the following: The photoconverter has a maximum absorption wavelength between 300 nm and 400 nm, and a maximum emission wavelength greater than 400 nm. In the above formula III, R １ This is a C in which at least one methylene group is substituted with -COO-. ３ ~C ２０ It is an alkyl group, R ２ and R ３ These are H and C, respectively, independently. １ ~C ２０ C is an alkyl group in which at least one methylene group is substituted with -COO-. ３ ~C ２０ One or more alkyl groups selected from the alkyl groups, If the general structural formula of the benzotriazole compound is the structure shown in formula III, the auxiliary agent includes a polyol compound.

2. If the general structural formula of the benzotriazole compound is the structure shown in formula I, then R １ and R ２ Each of these is independently a substituted or unsubstituted C. ５ ~C １０ C is an alkyl group in which at least one methylene group is substituted with -COO- or -O-. ５ ~C １０ alkyl, substituted or unsubstituted C ５ ~C １０ It is one selected from the alkenyl groups of the following; preferably the R １ and R ２ The photoconversion adhesive film composition according to claim 1, characterized in that each of the following groups is independently a group in which at least one methylene group of any of the following groups is independently substituted with -COO- or -O-, or one selected from pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group.

3. When the general structural formula of the benzotriazole compound is the structure shown in formula I, the benzotriazole derivative is 【Transformation 5】 【Transformation 6】 【Transformation 7】 One or more of the following are selected from R １ R ３ R ４ R ５ R ６ The photoconversion adhesive film composition according to claim 1 or 2, characterized in that each of the following groups is independently a group in which at least one methylene group of any of the following groups is independently substituted with -COO- or -O-, or a group selected from pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl groups.

4. If the general structural formula of the benzotriazole compound is the structure shown in formula I, then R １ The aforementioned R ３ The aforementioned R ４ The aforementioned R ５ The aforementioned R ６ The photoconversion adhesive film composition according to any one of claims 1 to 3, characterized in that each of them is independently one or more selected from tert-butyl group, octyl group, nonyl group, hexenyl group, heptenyl group, octenyl group, ethyl butyrate group, propyl butyrate group, butyl butyrate group, dipropyl ether, dibutyl ether, and butylpentyl ether.

5. The photoconversion adhesive film composition according to claim 3, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula I, the benzotriazole derivative includes benzotriazole derivatives having the structures shown in (I) and (II), and preferably the molar ratio of the benzotriazole derivatives having the structures shown in (I) and (II) is 1:0.01 to 0.

5.

6. The photoconversion adhesive film composition according to any one of claims 1 to 5, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula I, the auxiliary agent comprises a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005% to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005% to 5%.

7. The photoconversion adhesive film composition according to any one of claims 1 to 6, wherein the general structural formula of the benzotriazole compound is the structure shown in formula I, the auxiliary agent further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1% to 20%, preferably 0.5% to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

8. If the general structural formula of the benzotriazole compound is the structure shown in formula II, then R １ and any of the methylene groups in R are 【Transformation 8】 It is substituted with one of -COO- or -O-; preferably R' is directly bonded or C １ ~C ８ The alkylene group is R １ And R is independently a substituted or unsubstituted C. １ ~C ８ alkyl, substituted or unsubstituted C １ ~C ８ alkoxy group, substituted or unsubstituted C １ ~C ８ Ester group, substituted or unsubstituted C １ ~C ８ It is one of the amino groups selected from the R １ And R is independently C １ ~C ８ Linear alkyl group, C ３ ~C ８ branched alkyl group, C １ ~C ８ It is one selected from the alkoxy groups of the following; preferably the R １ And each of the R groups is independently a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, a butyl group, a butoxy group, a pentyl group, a pentyloxy group, a hexyl group, a hexyloxy group, a heptyl group, a heptyloxy group, an octyl group, an octyloxy group, a vinyl group, an allyl group, an alkenylbutyl group, an alkenylpentyl group, an alkenylhexyl group, an alkenylheptyl group, an alkenyloctyl group, 【Chemistry 9】 It is one of the following selected; further preferably, R1 and R are each independently an alkenyloctyl group, a heptyl group, 【Chemistry 10】 The photoconversion adhesive film composition according to claim 1, characterized in that it is one of the following selected from.

9. If the general structural formula of the benzotriazole compound is the structure shown in formula II, then R １ And R is a substituent that is terminally encapsulated with an unsaturated substituted functional group, preferably the unsaturated substituted functional group is one selected from an olefin group, an acrylic acid group, or an acrylic acid ester group, preferably the unsaturated substituted functional group is a vinyl group. and / or the R １ The photoconversion adhesive film composition according to claim 1 or 8, characterized in that, if R has a substituent, the substituent is one or more selected from a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, and a nitro group.

10. If the general structural formula of the benzotriazole compound is the structure shown in formula II, then R ２ and R ３ These are H and C, respectively, independently. １ ~C １０ C in which the hydrocarbon group, at least one methylene group is substituted with -COO- ３ ~C １０ One or more of the hydrocarbon groups selected from the R ２ and R ３ Each is independent of the others. 【Chemistry 11】 One or more of the following are selected, where "*" is the R ２ and R ３ The photoconversion adhesive film composition according to any one of claims 1, 8, or 9, characterized in that it represents the bonding site to each benzene ring.

11. When the general structural formula of the benzotriazole compound is the structure shown in formula II, the benzotriazole derivative is 【Chemistry 12】 A photoconversion adhesive film composition according to any one of claims 1, 8 to 10, characterized in that it is one or more selected from the following.

12. The photoconversion adhesive film composition according to any one of claims 1, 8 to 11, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula II, the auxiliary agent comprises a crosslinking agent and / or an auxiliary crosslinking agent; preferably, the weight percentage of the crosslinking agent is 0.005% to 5%, and / or the weight percentage of the auxiliary crosslinking agent is 0.005% to 5%.

13. The photoconversion adhesive film composition according to any one of claims 1, 8 to 12, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula II, the auxiliary further comprises a polyol compound, preferably the mass of hydroxyl groups in the polyol compound is 0.1% to 20%, preferably 0.5% to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

14. If the general structural formula of the benzotriazole compound is the structure shown in formula III, then, when calculated by weight percentage, the photoconversion adhesive film composition is The matrix resin comprising 98% to 99.98%, A 0.01% to 1% of the aforementioned photoconverter, The above-mentioned auxiliary agent is present in an amount of 0.01% to 1%, Furthermore, the photoconverting adhesive film composition according to claim 1 is characterized in that the mass ratio of the photoconverting agent to the auxiliary agent is preferably 1:2 to 500, and more preferably 1:2 to 50.

15. The photoconversion adhesive film composition according to claim 1 or 14, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula III, the mass of the hydroxyl group in the polyol compound is 0.1% to 20%, preferably 0.5% to 10%, of the mass of the polyol compound, preferably the molecular weight of the polyol compound is 500 to 80000, and preferably the polyol compound is one or more selected from polyvinyl alcohol compounds, polyethylene glycol, and polypropylene glycol.

16. When the general structural formula of the benzotriazole-based compound is the structure shown in Formula III, the auxiliary agent further includes a polyester-based compound. Preferably, the molecular weight of the polyester-based compound is 500 to 80,000. Preferably, the mass ratio of the polyol-based compound to the polyester-based compound is 1:0.01 to 1. Preferably, the mass ratio of the polyol-based compound to the polyester-based compound is 1:0.1 to 0.

5. Preferably, the polyester-based compound is an aliphatic polyester and / or an aromatic polyester. Preferably, the aromatic polyester is polyethylene terephthalate. Preferably, the aliphatic polyester is C ２ ~C １２ An aliphatic dibasic acid and C ２ ~C １２ Any one or more selected from polyester-based compounds and polyurethanes obtained by polymerization of alkyldiols. Preferably, the aliphatic polyester is any one or more selected from polyurethanes, polybutylene succinate, polymethyl methacrylate, polyethylene glycol ester, and polyhydroxybutyrate. The light-converting adhesive film composition according to any one of claims 1, 14 or 15, characterized by this.

17. When the general structural formula of the benzotriazole-based compound is the structure shown in Formula III, the R １ is an alkyl group of C ３ to C １０ in which at least one methylene group is substituted with -COO-, and preferably the R １ is 【Chemistry 13】 One or more selected from, where "*" is the R of the benzotriazole compound. １ The portion excluding and the R １ A photoconversion adhesive film composition according to any one of claims 1, 14 to 16, characterized in that it represents a bonding site with

18. If the general structural formula of the benzotriazole compound is the structure shown in formula III, then R ２ and R ３ These are H and C, respectively, independently. １ ~C １０ C is an alkyl group in which at least one methylene group is substituted with -COO-. ３ ~C １０ One or more selected from the alkyl groups, preferably the R ２ and R ３ Each is independent of the others. 【Chemistry 14】 One or more of the following are selected, where "*" is the R of the benzotriazole compound. ２ The portion excluding and the R ２ This represents the connection site, More preferably, the R ２ is the aforementioned R ３ It is the same as, and preferably the benzotriazole compound is 【Chemistry 15】 The photoconversion adhesive film composition according to any one of claims 1, 14 to 17, characterized in that it is one or more selected from the above.

19. The photoconverting adhesive film composition according to any one of claims 1, 14 to 18, characterized in that, when the general structural formula of the benzotriazole compound is the structure shown in formula III, the total mass of the matrix resin, the photoconverter and the auxiliary agent is calculated as 100%, the photoconverting adhesive film composition further contains 0.01% to 1% of a crosslinking agent, preferably 0.01% to 0.5%.

20. The photoconversion adhesive film composition according to any one of claims 1 to 19, characterized in that the matrix resin is one or more selected from EVA, PVA, PMMA, POE, and silicone.

21. A photoconverting adhesive film prepared by mixing and molding an adhesive film composition, wherein the adhesive film composition is a photoconverting adhesive film composition according to any one of claims 1 to 20.

22. A photovoltaic module comprising a photoconversion adhesive film, wherein the photoconversion adhesive film is the photoconversion adhesive film described in claim 21.

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