Light conversion adhesive film composition, light conversion adhesive film and photovoltaic module

Abstract

The invention provides a light conversion adhesive film composition, a light conversion adhesive film and a photovoltaic module. The light conversion adhesive film composition comprises the following components in parts by weight: 100 parts of matrix resin, 0.01-10 parts of an organic polymer light conversion agent and 0.01-10 parts of an auxiliary agent, the organic polymer light conversion agent is formed by copolymerization of a light conversion agent monomer shown in a formula I and a silane coupling agent containing a carbon-carbon double bond, # imgabs0, R1 is substituted or non-substituted C2-C30 alkyl, and R1 at least comprises a terminal carbon-carbon double bond; r < 2 > and R < 3 > are respectively and independently selected from any one of substituted or non-substituted alkyl of C1 to C30, substituted or non-substituted alkoxy of C1 to C30, substituted or non-substituted aryl of C6 to C30, substituted or non-substituted heteroaryl of C4 to C30, amido, carboxyl and hydroxyl; according to the technical scheme, the problems that a preparation method of the high-stability light conversion agent is complex in preparation process and high in cost are solved.

Description

Technical Field

[0001] The present invention relates to the field of optoelectronic technology, and in particular to a light-converting adhesive film composition, a light-converting adhesive film and a photovoltaic module. Background Art

[0002] Solar cells can convert sunlight into electricity, offering a practical and effective solution to the energy crisis. However, existing crystalline silicon solar cells only have high conversion efficiency for visible sunlight, with very low efficiency for ultraviolet light, which can even irreversibly damage some cells.

[0003] Light conversion agents convert ultraviolet light from sunlight into visible light, which can then be incorporated into photovoltaic films to create a light conversion film. This not only improves the solar light conversion efficiency of photovoltaic modules but also protects the cells from UV damage, extending their service life. Light conversion agents are generally categorized into three main types: organic, inorganic, and organic-inorganic composites. Compared to inorganic and organic-inorganic composites, organic light conversion agents offer significant advantages in terms of light conversion efficiency, film compatibility, and compatibility with existing additive systems, making them a key area of research for practitioners. However, organic light conversion agents are sensitive to water and oxygen and exhibit poor stability. Prolonged exposure to sunlight and water and oxygen can lead to their ineffectiveness. Therefore, improving organic light conversion agents to achieve more stable performance and enhance the adhesion of photovoltaic films to block water and oxygen is crucial.

[0004] Currently, grafting requires chemical changes at the resin level, which places high demands on equipment, process complexity, and cost. Improving adhesion through a multi-layer approach requires co-extrusion, which is costly and can lead to additive migration between layers. Directly altering the structure of the light-converting agent requires a molecular redesign, significantly altering the original synthesis route, resulting in high costs and complex, time-consuming experimental procedures. Summary of the Invention

[0005] One of the main purposes of the present invention is to provide a light-converting adhesive film composition, a light-converting adhesive film and a photovoltaic module to solve the problems of complex preparation process and high cost in the prior art preparation method of high-stability light-converting agents.

[0006] To achieve the above object, according to one aspect of the present invention, a light-converting adhesive film composition is provided, which comprises, by weight, 100 parts of a base resin, 0.01 to 10 parts of an organic polymer light-converting agent, and 0.01 to 10 parts of an auxiliary agent; wherein the organic polymer light-converting agent is copolymerized by a light-converting agent monomer represented by Formula I and a silane coupling agent containing a carbon-carbon double bond.

[0007]

[0008]

[0009] Wherein, R1 is substituted or unsubstituted C2~C 30 and R1 includes at least a terminal carbon-carbon double bond; R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C1~C 30 Alkoxy, substituted or unsubstituted C6~C 30 aryl, substituted or unsubstituted C4~C 30 any one of heteroaryl, amide, carboxyl and hydroxyl groups; n is any integer from 1 to 10; the maximum absorption wavelength of the organic polymer light conversion agent is between 325 and 375 nm, and the maximum emission wavelength is between 400 and 450 nm.

[0010] Furthermore, the above n is any integer from 1 to 6; and / or, one or more methylene groups in R1, R2 and R3 are each independently substituted by -COO-, -O- or -S-; and / or, when R1, R2 and R3 have substituents, the substituents are each independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, -COO-, and nitro.

[0011] Furthermore, the above R1 is substituted or unsubstituted C2 to C 20 The hydrocarbon group, preferably R1 is substituted or unsubstituted C3~C 15 The hydrocarbon group, further, preferably, the terminal carbon-carbon double bond in R1 is a terminal carbon-carbon double bond containing a substituent, preferably the terminal carbon-carbon double bond containing a substituent is CH2=CH-COO- and / or CH2=C(CH3)-COO-; preferably, R1 is selected from

[0012] Any one of .

[0013] Furthermore, the above R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 20 C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 20 aryl, substituted or unsubstituted C4~C 20 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 12 C1~C12 Alkyl, substituted or unsubstituted C1~C 12 Alkoxy, substituted or unsubstituted C6~C 12 aryl, substituted or unsubstituted C4~C 12 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 12 C5~C 12 Alkyl, substituted or unsubstituted C5~C 12 Alkoxy, substituted or unsubstituted C6~C 10 aryl, substituted or unsubstituted C4~C 10 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 10 C5~C 10 alkyl, substituted or unsubstituted phenyl; further preferably, R2 and R3 are each independently selected from a group in which at least one methylene group of any one of pentyl, hexyl, heptyl, octyl, nonyl and decyl is independently substituted by -COO- or -O-, any one of pentyl, hexyl, heptyl, octyl, nonyl, decyl, amide, carboxyl and hydroxyl.

[0014] Furthermore, the structural formula of the light conversion agent monomer is R4 and R5 are each independently selected from H, C1-C 20 C3~C 20 Preferably R4 and R5 are each independently selected from C1 to C 10 C3~C 10 Any one or more of the alkyl groups, preferably R4 and R5 are each independently selected from

[0015] Any one or more of the following, wherein “*” represents the connection site on the benzene ring where R4 and R5 are located.

[0016] Furthermore, the molecular weight of the organic polymer light conversion agent is 1000 to 50000 g / mol, preferably 5000 to 40000 g / mol, further preferably 15000 to 40000 g / mol, and the light conversion agent monomer is preferably selected from

[0017]

[0018]

[0019] Any one or more of .

[0020] Furthermore, the above-mentioned silane coupling agent containing a carbon-carbon double bond is selected from any one or more of γ-methacryloxypropyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 5-hexenyltrimethoxysilane, allyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 10-alkenylundecyltrimethoxysilane, vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, acrylamidopropyltrimethoxysilane, allyltriethoxysilane, 11-allyloxyundecyltrimethoxysilane, methacryloxymethyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane.

[0021] Furthermore, the above-mentioned base resin is selected from any one or more of EVA, PVA, PMMA, POE, PVB, and silicone; and / or the auxiliary agent includes any one or more of hindered amine light stabilizers, organic peroxides, cross-linking agents and adhesives; and / or the hindered amine light stabilizer is 0.01 to 10 parts by weight; and / or the organic peroxide is 0.01 to 2 parts by weight; and / or the cross-linking agent is 0.01 to 3 parts by weight; and / or the adhesive is 0.01 to 3 parts by weight.

[0022] According to another aspect of the present invention, a light-converting adhesive film is provided, which includes the light-converting adhesive film composition described above.

[0023] According to another aspect of the present invention, a photovoltaic module is provided, comprising a light conversion adhesive film, wherein the light conversion adhesive film is the aforementioned light conversion adhesive film.

[0024] Using the technical solution of the present invention, a small molecule light-converting agent containing a benzotriazole structure is copolymerized with a silane coupling agent to produce an organic polymer light-converting agent. The substituents corresponding to the silane coupling agent in the organic polymer light-converting agent help improve its adhesion. Furthermore, after polymerization, the benzotriazole structure corresponding to the light-converting agent monomer is encapsulated within the substituent structure corresponding to the silane coupling agent, further preventing contact between water and oxygen and the benzotriazole structure, thereby improving the stability of the light-converting agent. Furthermore, the high molecular weight of the organic polymer light-converting agent enhances the adhesion of the composition containing it after it is formed into an adhesive film, thereby reducing the risk of light-converting agent migration. Furthermore, due to the good compatibility of the organic polymer light-converting agent with the matrix resin, it can be directly mixed with the matrix resin, thereby improving the compatibility of the overall light-converting adhesive film composition. This solution also exhibits excellent compatibility with existing adhesive film systems, thereby addressing the complex and costly preparation process for highly stable light-converting agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0026] Figure 1 shows an absorption intensity diagram of the organic polymer light conversion agent 1 in Example 1 of the present invention;

[0027] Figure 2 shows an emission intensity diagram of the organic polymer light conversion agent 1 in Example 1 of the present invention;

[0028] Figure 3 It shows the absorption intensity graph of the light conversion agent monomer 1 in Comparative Example 1 according to the present invention;

[0029] Figure 4 The emission intensity graph of the light converter monomer 1 in Comparative Example 1 according to the present invention is shown. DETAILED DESCRIPTION

[0030] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0031] As analyzed in the background technology of this application, the preparation method of high-stability light conversion agent in the prior art has the problems of complex preparation process and high cost. In order to solve this technical problem, this application provides a light conversion adhesive film composition, a light conversion adhesive film and a photovoltaic module.

[0032] In a typical embodiment of the present application, a light-converting adhesive film composition is provided, which comprises, by weight percentage, 100 parts of a base resin, 0.01 to 10 parts of an organic polymer light-converting agent, and 0.01 to 10 parts of an auxiliary agent; wherein the organic polymer light-converting agent is copolymerized by a light-converting agent monomer represented by Formula I and a silane coupling agent containing a carbon-carbon double bond.

[0033]

[0034] Wherein, R1 is substituted or unsubstituted C2~C 30 and R1 includes at least a terminal carbon-carbon double bond; R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C1~C 30 Alkoxy, substituted or unsubstituted C6~C 30 aryl, substituted or unsubstituted C4~C 30 any one of heteroaryl, amide, carboxyl and hydroxyl groups; n is any integer from 1 to 10; the maximum absorption wavelength of the organic polymer light conversion agent is between 325 and 375 nm, and the maximum emission wavelength is between 400 and 450 nm.

[0035] A small molecule light-converting agent containing a benzotriazole structure is copolymerized with a silane coupling agent to produce an organic polymer light-converting agent. The substituents corresponding to the silane coupling agent in the organic polymer light-converting agent enhance its adhesion. Furthermore, after polymerization, the benzotriazole structure corresponding to the light-converting agent monomer is encapsulated within the substituent structure corresponding to the silane coupling agent, further preventing contact between water and oxygen and the benzotriazole structure, thereby improving the stability of the light-converting agent. Furthermore, the high molecular weight of the organic polymer light-converting agent enhances the adhesion of the composition formed into an adhesive film, thereby reducing the risk of light-converting agent migration. Furthermore, due to the good compatibility of the organic polymer light-converting agent with the matrix resin, it can be directly mixed with the matrix resin, thereby improving the overall compatibility of the light-converting adhesive film composition. This solution also exhibits excellent compatibility with existing adhesive film systems, thereby addressing the complex and costly preparation process for highly stable light-converting agents.

[0036] In one embodiment of the present application, the above-mentioned n is any integer from 1 to 6; and / or, one or more methylene groups in R1, R2 and R3 are independently substituted by -COO-, -O- or -S-; and / or, when R1, R2 and R3 have substituents, the substituents are independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, -COO-, and nitro.

[0037] The preferred types of substituents above help to further increase the richness of R1, R2 and R3 substituents on the peripheral modification of the benzotriazole benzene ring, thereby better obtaining an organic polymer light conversion agent with higher comprehensive light conversion efficiency under the synergistic effect of each group.

[0038] In one embodiment of the present application, the above R1 is substituted or unsubstituted C2 to C 20 The hydrocarbon group, preferably R1 is substituted or unsubstituted C3~C 15 The hydrocarbon group, further, preferably the terminal carbon-carbon double bond in R1 is a terminal carbon-carbon double bond containing a substituent, preferably the terminal carbon-carbon double bond containing a substituent is CH2=CH-COO- and / or CH2=C(CH3)-COO-; preferably R1 is selected from

[0039] Any one of .

[0040] The terminal double bond of the preferred R1 substituent has higher reactivity, thereby helping to improve the efficiency and effect of copolymerization of the light conversion agent monomer with the silane coupling agent containing a carbon-carbon double bond, thereby obtaining an organic polymer light conversion agent with better performance.

[0041] In one embodiment of the present application, the above R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 20 C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 20 aryl, substituted or unsubstituted C4~C 20 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 12 C1~C 12 Alkyl, substituted or unsubstituted C1~C 12 Alkoxy, substituted or unsubstituted C6~C 12 aryl, substituted or unsubstituted C4~C 12 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 12 C5~C 12 Alkyl, substituted or unsubstituted C5~C 12 Alkoxy, substituted or unsubstituted C6~C 10 aryl, substituted or unsubstituted C4~C10 Any one of heteroaryl, amide, carboxyl, and hydroxyl; preferably, R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 10 C5~C 10 alkyl, substituted or unsubstituted phenyl; further preferably, R2 and R3 are each independently selected from a group in which at least one methylene group of any one of pentyl, hexyl, heptyl, octyl, nonyl and decyl is independently substituted by -COO- or -O-, any one of pentyl, hexyl, heptyl, octyl, nonyl, decyl, amide, carboxyl and hydroxyl.

[0042] The preferred R2 and R3 are more conducive to the synergistic effect between the two, such as improving the interaction between R2, R3 and the matrix resin, such as hydrogen bonding, thereby enhancing the compatibility of the above organic polymer light conversion agent and the matrix resin, and providing a more favorable protective layer for the luminescent core structure.

[0043] In one embodiment of the present application, the structural formula of the light conversion agent monomer is R4 and R5 are each independently selected from H, C1-C 20 C3~C 20 Preferably R4 and R5 are each independently selected from C1 to C 10 Alkyl, at least one methylene group is substituted by -COO-

[0044] Any one or more of the following, wherein “*” represents the connection site on the benzene ring where R4 and R5 are located.

[0045] The preferred light conversion agent monomer with the above structure is more conducive to improving its synergistic coordination with the silane coupling agent, thereby making the organic polymer light conversion agent have a higher light conversion efficiency.

[0046] In order to improve the photostability of the organic polymer light conversion agent, reduce its mobility, and take into account its excellent light conversion efficiency and other properties, the molecular weight of the organic polymer light conversion agent is preferably 1000-50000 g / mol, preferably 5000-40000 g / mol, further preferably 15000-40000 g / mol, and the light conversion agent monomer is preferably selected from

[0047]

[0048] Any one or more of .

[0049] In one embodiment of the present application, the above-mentioned silane coupling agent containing a carbon-carbon double bond is selected from any one or more of γ-methacryloxypropyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 5-hexenyltrimethoxysilane, allyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 10-alkenylundecyltrimethoxysilane, vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, acrylamidopropyltrimethoxysilane, allyltriethoxysilane, 11-allyloxyundecyltrimethoxysilane, methacryloxymethyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane.

[0050] The preferred silane coupling agent containing a carbon-carbon double bond is more conducive to improving its reactivity with the light conversion agent monomer, and through its rich functional groups, it improves the overall adhesion of the organic polymer light conversion agent, improves the compatibility of the organic polymer light conversion agent in the light conversion agent composition system, and reduces the mobility of the organic polymer light conversion agent.

[0051] In addition, the polymerization of the light conversion agent monomer and the silane coupling agent containing a carbon-carbon double bond in the present application includes any one of free radical polymerization, anionic polymerization, and cationic polymerization, preferably free radical polymerization. The polymerization forms include solution polymerization or emulsion polymerization, preferably solution polymerization.

[0052] In one embodiment of the present application, the above-mentioned base resin is selected from any one or more of EVA, PVA, PMMA, POE, PVB, and silicone; and / or, the auxiliary agent includes any one or more of a hindered amine light stabilizer, an organic peroxide, a cross-linking agent and an adhesive; and / or, the hindered amine light stabilizer is 0.01 to 10 parts by weight; and / or, the organic peroxide is 0.01 to 2 parts by weight; and / or, the cross-linking agent is 0.01 to 3 parts by weight; and / or, the adhesive is 0.01 to 3 parts by weight.

[0053] The preferred matrix resin mentioned above helps to better cooperate with components such as the light-converting agent to obtain a light-converting film with excellent performance. The above matrix resin is cheap and helps to reduce costs. Of course, those skilled in the art can also use other matrix resins, which will not be repeated here.

[0054] The co-crosslinking agent is a molecule having multiple ethylenically unsaturated groups, which can promote the crosslinking of the polymer to achieve a higher degree of crosslinking. Preferably, the co-crosslinking agent is selected from triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, Any one or more of acrylate, ditrimethylolpropane tetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclodecane dimethanol 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.

[0055] The addition of an adhesive can improve the bonding performance between the film and the substrate. In a preferred embodiment, the adhesive includes, but is not limited to, one or more of the group consisting of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethylsilane, and 3-aminopropyltrimethylsilane.

[0056] The preferred hindered amine light stabilizer is beneficial to further improve the stability of the light-converting adhesive film composition system. The preferred hindered amine light stabilizer is selected from any one or more of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite sebacate bis-2,2,6,6-tetramethylpiperidinol ester, bis-1-decyloxy-2,2,6,6-tetramethylpiperidin-4-ol sebacate, polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, and polymer of morpholine-2,4,6-trichloro-1,3,5-triazine.

[0057] Preferably, an organic peroxide is added so that the light-converting adhesive film composition system is a free radical polymerization system. The preferred organic peroxide is selected from any one or more combinations of diacyl peroxide, dialkyl peroxide, peroxyester, and peroxyketal; the preferred peroxyester is selected from 3,3-bis(tert-butylperoxy)ethyl butyrate, 3,3-bis(tert-amylperoxy)ethyl butyrate, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexyl carbonate, n-butyl 4,4-bis(tert-butylperoxy)valerate, tert-amyl peroxybenzoate, tert-amyl peroxyacetate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexyl carbonate A combination of any one or more of tert-amyl ester, tert-amyl peroxyisobutyrate, and 2,5-dimethyl-2,5-bis(benzoylperoxy)-hexane; preferably, the diacyl peroxide is selected from a combination of any one or more of benzoyl peroxide, lauric peroxide, and decanoic peroxide; preferably, the peroxyketal is selected from a combination of any one or more of 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, and 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane; preferably, the dialkyl peroxide is dicumyl peroxide and / or 2,5-dimethyl-2,5-bis-(tert-butylperoxy)hexane.

[0058] In another typical embodiment of the present application, a light-converting adhesive film is provided, wherein the light-converting adhesive film comprises the light-converting adhesive film composition described above.

[0059] In some preferred embodiments of the present application, after the aforementioned light-converting adhesive film composition is evenly mixed, a light-converting adhesive film is prepared by a preparation process such as melt extrusion molding at 80-120°C. The obtained light-converting adhesive film has both excellent stability and high luminous efficiency, and can effectively function for a long time, thereby improving the service life of the photovoltaic device.

[0060] In another typical embodiment of the present application, a photovoltaic module is provided, comprising a light-converting adhesive film, which is the light-converting adhesive film described above.

[0061] The photovoltaic module including the above-mentioned light-converting film of the present application has excellent light-converting efficiency. Of course, there are more choices according to different needs and application scenarios. The light-converting film of the present application is not limited to photovoltaic devices, agricultural films, architectural glass and other fields.

[0062] Typically, a photovoltaic module comprises crystalline silicon solar cells, a front glass panel, a rear glass panel or a polymer backsheet, and a light-converting adhesive film positioned between the front glass panel and the solar cells. The light-converting adhesive film positioned between the front glass panel and the solar cells is the light-converting adhesive film of the present application. The light-converting adhesive film positioned between the rear glass panel or polymer backsheet and the solar cells can be the light-converting adhesive film of the present application or any other conventional encapsulating adhesive film in the prior art.

[0063] The beneficial effects of the present application will be further illustrated below with reference to examples.

[0064] Example 1

[0065] The light-converting adhesive film composition comprises, by weight, 100 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of an organic polymer light-converting agent 1, 0.5 parts by weight of a cross-linking agent, tert-butyl peroxyisopropyl carbonate, and 0.5 parts by weight of a co-cross-linking agent, trimethylolpropane tetraacrylate. The organic polymer light-converting agent is copolymerized with a silane coupling agent containing a carbon-carbon double bond. The synthesis route of the light-converting agent monomer 1 (i.e., T3) is as follows:

[0066]

[0067] 1. Synthesis of T1

[0068] A mixture of benzotriazole (2 g, 16.8 mmol), 6-chlorohexyl acrylate (3.81 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 organic phase obtained was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product as a transparent oily droplet. The product was separated and purified by column chromatography using a petroleum ether / dichloromethane mixture as the eluent to obtain 2.98 g of the pure product as a light yellow oil, with a yield of 65%.

[0069] 2. Synthesis of T2

[0070] T1 (2 g, 7.3 mmol) was dissolved in 20 mL of nitric acid and heated. With stirring, bromine (2.6 g, 16 mmol) was slowly added dropwise to the reaction system, and the mixture was refluxed and stirred for 24 h. The reaction was quenched with saturated aqueous sodium bisulfite solution. The precipitated solid was washed with water and filtered to obtain a crude off-white powder. The product was recrystallized from dichloromethane to obtain 2.2 g of a white solid powder, with a yield of 70%.

[0071] Synthesis of T3

[0072] T2 (2 g, 4.6 mmol), 4-tert-butylphenylboronic acid (2 g, 11.2 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 the atmosphere was purged with nitrogen. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. Stir and heat under reflux for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Purification was performed by column chromatography using ethyl acetate / petroleum ether as the eluent to obtain 1.73 g of a white solid product in a 70% yield.

[0073] 10 g of the light conversion agent monomer 1 and 10 g of 3-(trimethoxysilyl)propyl acrylate coupling agent were dissolved in 100 mL of xylene, 0.05 g of azobisisobutyronitrile as an initiator was added, and the mixture was reacted at 60° C. for 24 h. The solvent was removed by rotary evaporation to obtain an organic polymer light conversion agent 1 having a molecular weight of 40,000 g / mol. The absorption intensity diagram and emission intensity diagram of the organic polymer light conversion agent 1 are shown in FIG. Figure 1 and Figure 2 shown.

[0074] The light-converting adhesive film composition was mixed evenly, and then melted and extruded at 90° C. to form a film, thereby obtaining a light-converting adhesive film.

[0075] Example 2

[0076] The light-converting adhesive film composition comprises, by weight, 100 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of an organic polymer light-converting agent 2, 0.5 parts by weight of a cross-linking agent (tert-butyl peroxyisopropyl carbonate), and 0.5 parts by weight of a co-cross-linking agent (trimethylolpropane tetraacrylate). The organic polymer light-converting agent is copolymerized with a silane coupling agent containing a carbon-carbon double bond. The synthesis route of the light-converting agent monomer 2 (i.e., T3) is as follows:

[0077]

[0078] 1. Synthesis of T1

[0079] A mixture of benzotriazole (2 g, 16.8 mmol), 7-chlorohept-1-en-3-one (2.93 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 organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain the crude product as a clear oily droplet. The product was separated and purified by column chromatography using a petroleum ether / dichloromethane mixture as the eluent to obtain 2.31 g of the pure product as a light yellow oil, with a yield of 60%.

[0080] 2. Synthesis of T2

[0081] T1 (2 g, 8.7 mmol) was dissolved in 20 mL of nitric acid and heated. Bromine (2.88 g, 18 mmol) was slowly added dropwise to the reaction system with stirring, and the mixture was refluxed and stirred for 24 h. The reaction was quenched with saturated aqueous sodium bisulfite solution. The precipitated solid was washed with water and filtered to obtain a crude off-white powder. The product was recrystallized from dichloromethane to obtain 2.53 g of a white solid powder, a yield of 75%.

[0082] Synthesis of T3

[0083] T2 (2 g, 5.2 mmol), 4-tert-butylphenylboronic acid (2.14 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 the atmosphere was purged with nitrogen. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. Stir and heat under reflux for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Purification was performed by column chromatography using ethyl acetate / petroleum ether as the eluent to obtain 1.67 g of a white solid product in a 65% yield.

[0084] 10 g of the light conversion agent monomer 2 and 10 g of a coupling agent containing 3-(trimethoxysilyl)propyl acrylate were dissolved in 100 mL of xylene, 0.05 g of an initiator, azobisisobutyronitrile, was added, and the mixture was reacted at 60° C. for 24 h. The solvent was removed by rotary evaporation to obtain an organic polymer light conversion agent 2 with a molecular weight of 20,000 g / mol.

[0085] The light-converting adhesive film composition was mixed evenly, and then melted and extruded at 90° C. to form a film, thereby obtaining a light-converting adhesive film.

[0086] Example 3

[0087] The light-converting adhesive film composition comprises, by weight, 100 parts by weight of ethylene vinyl acetate, 0.2 parts by weight of an organic polymer light-converting agent 3, 0.5 parts by weight of a cross-linking agent (tert-butyl peroxyisopropyl carbonate), and 0.5 parts by weight of a co-cross-linking agent (trimethylolpropane tetraacrylate). The organic polymer light-converting agent is copolymerized with a silane coupling agent containing a carbon-carbon double bond. The synthesis route of the light-converting agent monomer 3 (i.e., T5) is as follows:

[0088]

[0089] 1. T1 synthesis

[0090] A mixture of benzotriazole (2 g, 16.8 mmol), 6-chlorohept-1-en-3-one (2.65 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 organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain the crude product as a clear oily droplet. The product was separated and purified by column chromatography using a petroleum ether / dichloromethane mixture as the eluent to obtain 2.53 g of the pure product as a light yellow oil, with a yield of 70%.

[0091] 2. Synthesis of T2

[0092] T1 (2 g, 9.3 mmol) was dissolved in 20 mL of nitric acid and heated. Bromine (3.20 g, 20 mmol) was slowly added dropwise to the reaction system with stirring, and the mixture was refluxed and stirred for 24 h. The reaction was quenched with saturated aqueous sodium bisulfite solution. The precipitated solid was washed with water and filtered to obtain a crude off-white powder. The product was recrystallized from dichloromethane to obtain 2.43 g of a white solid powder, a 70% yield.

[0093] 3. Synthesis of T3

[0094] T2 (2 g, 5.4 mmol), 4-tert-butylphenylboronic acid (0.89 g, 5 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 the atmosphere was purged with nitrogen. 18 mL of toluene and 12 mL of deionized water were added to the reaction system. Stir and heat under reflux for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification using ethyl acetate / petroleum ether as the eluent to obtain 1.38 g of a white solid product in a 65% yield.

[0095] 4. Synthesis of T4

[0096] 1,4-Benzenediboronic acid (2g, 12mmol), potassium carbonate (6.6g, 48mmol), and tetrakistriphenylphosphine palladium (0.4g, 0.36mmol) were mixed in a two-necked flask and the atmosphere was purged with nitrogen. Ethyl 4-bromobutyrate (2.3g, 12mmol), 18mL of toluene, and 12mL of deionized water were added to the reaction system. Stir and heat under reflux for 24h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Purification by column chromatography using ethyl acetate / petroleum ether as the eluent yielded 1.98g of the product as a white solid in a 70% yield.

[0097] 5. Synthesis of T5

[0098] T4 (0.71 g, 3 mmol), T3 (1 g, 2.3 mmol), potassium carbonate (1.5 g, 10.8 mmol), and tetrakistriphenylphosphine palladium (0.1 g, 0.09 mmol) were mixed in a two-necked flask and the atmosphere was purged with nitrogen. 9 mL of toluene and 6 mL of deionized water were added to the reaction system. Stir and heat under reflux for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Purification was performed by column chromatography using ethyl acetate / petroleum ether as the eluent to obtain 0.93 g of the product as a white solid in a 75% yield.

[0099] 10 g of the light conversion agent monomer 3 and 10 g of a coupling agent containing 3-(trimethoxysilyl)propyl acrylate were dissolved in 100 mL of xylene, and 0.05 g of an initiator, azobisisobutyronitrile, was added. The mixture was reacted at 60° C. for 24 h, and the solvent was removed by rotary evaporation to obtain an organic polymer light conversion agent 3 with a molecular weight of 8000 g / mol.

[0100] The light-converting adhesive film composition was mixed evenly, and then melted and extruded at 90° C. to form a film, thereby obtaining a light-converting adhesive film.

[0101] Example 4

[0102] The difference from Example 1 is that 10 g of the light conversion agent monomer 1 and 5 g of a coupling agent containing 3-(trimethoxysilyl)propyl acrylate were dissolved in 100 mL of xylene, 0.05 g of an initiator, azobisisobutyronitrile, was added, and the mixture was reacted at 80° C. for 10 h. The solvent was removed by rotary evaporation to obtain an organic polymer light conversion agent 4 with a molecular weight of 15,000 g / mol, and finally a light conversion adhesive film was obtained.

[0103] Example 5

[0104] The difference from Example 1 is that 10 g of the light conversion agent monomer 1 and 2 g of a coupling agent containing 3-(trimethoxysilyl)propyl acrylate were dissolved in 100 mL of xylene, 0.05 g of an initiator, azobisisobutyronitrile, was added, and the mixture was reacted at 80° C. for 10 h. The solvent was removed by rotary evaporation to obtain an organic polymer light conversion agent 5 with a molecular weight of 5000 g / mol, and finally a light conversion adhesive film was obtained.

[0105] Example 6

[0106] The difference from Example 1 is that, in parts by weight, the light-converting adhesive film composition includes 100 parts by weight of ethylene vinyl acetate, 0.01 parts by weight of an organic polymer light-converting agent 1, 0.01 parts by weight of γ-methacryloxypropyltrimethoxysilane, 0.01 parts by weight of tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite bis-2,2,6,6-tetramethylpiperidinol sebacate, 0.01 parts by weight of a crosslinking agent tert-butyl peroxyisopropyl carbonate, and 0.01 parts by weight of a co-crosslinking agent trimethylolpropane tetraacrylate, to finally obtain a light-converting adhesive film.

[0107] Example 7

[0108] The difference from Example 1 is that, in parts by weight, the light-converting adhesive film composition includes 100 parts by weight of ethylene vinyl acetate, 10 parts by weight of an organic polymer light-converting agent 1, 3 parts by weight of γ-methacryloxypropyltrimethoxysilane, 10 parts by weight of tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite bis-2,2,6,6-tetramethylpiperidinol sebacate, 2 parts by weight of a crosslinking agent tert-butyl peroxyisopropyl carbonate, and 3 parts by weight of a co-crosslinking agent trimethylolpropane tetraacrylate, to finally obtain a light-converting adhesive film.

[0109] Example 8

[0110] The difference from Example 1 is that, based on parts by weight, the base resin is ethylene-1-octene copolymer, and a light-converting adhesive film is finally obtained.

[0111] Comparative Example 1

[0112] The difference from Example 1 is that the light conversion agent monomer 1 is directly used as the light conversion agent to finally obtain a light conversion adhesive film. The absorption intensity diagram and emission intensity diagram of the light conversion agent monomer 1 are respectively as follows: Figure 3 and Figure 4 shown.

[0113] Comparative Example 2

[0114] The difference from Example 1 is that the light conversion agent is a benzotriazole compound, and its structural formula is as follows:

[0115]

[0116] , and finally obtain the light-converting film.

[0117] Comparative Example 3

[0118] The difference from Example 3 is that, in parts by weight, the light-converting adhesive film composition includes 90 parts by weight of a base resin, 15 parts by weight of an organic polymer light-converting agent 3, 0.5 parts by weight of a cross-linking agent tert-butyl peroxyisopropyl carbonate, and 0.5 parts by weight of a co-cross-linking agent trimethylolpropane tetraacrylate, to finally obtain a light-converting adhesive film.

[0119] Test Method

[0120] Light conversion efficiency: Horiba spectrometer FL-3, absolute quantum efficiency test was performed using an integrating sphere at room temperature.

[0121] Stability test: The obtained photovoltaic film was subjected to ultraviolet radiation aging test according to the requirements of the International Electrotechnical Commission standard IEC61345. Test conditions: the surface temperature of the test piece is 60±5℃, the ultraviolet wavelength range is 280~400nm, and the irradiation intensity is 15kW·h / m 2 The UV irradiation test duration was 2000 hours. The light conversion efficiency was measured before and after the test, with the light conversion efficiency before the test as T0% and the light conversion efficiency after the test as T1%. W% was calculated as T1% / T0%*100%. A higher W% indicates better stability of the light conversion agent.

[0122] Adhesion: The test method refers to the standard GB / T 29848 "Ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module encapsulation".

[0123] Test method for light conversion agent migration distance: arrange glass, the above-mentioned packaging film, silicon heterojunction battery (Huasheng), UV-transmissive packaging film (Foster F406P), and glass in order from bottom to top to obtain a stack, place the stack in a vacuum laminator, and press at 145°C for 15 minutes to obtain a solar module; the modules are allowed to stand at 25°C for 6 hours, and then placed in a 120°C oven for 144 hours to evaluate the distance (unit / cm) that the light conversion agent migrates from the edge of the battery cell to the back of the battery cell. The larger the distance, the more serious the migration of the light conversion agent.

[0124] The above test results are listed in Table 1.

[0125] Table 1

[0126]

[0127]

[0128] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0129] A small molecule light-converting agent containing a benzotriazole structure is copolymerized with a silane coupling agent to produce an organic polymer light-converting agent. The substituents corresponding to the silane coupling agent in the organic polymer light-converting agent enhance its adhesion. Furthermore, after polymerization, the benzotriazole structure corresponding to the light-converting agent monomer is encapsulated within the substituent structure corresponding to the silane coupling agent, further preventing contact between water and oxygen and the benzotriazole structure, thereby improving the stability of the light-converting agent. Furthermore, the high molecular weight of the organic polymer light-converting agent enhances the adhesion of the composition formed into an adhesive film, thereby reducing the risk of light-converting agent migration. Furthermore, due to the good compatibility of the organic polymer light-converting agent with the matrix resin, it can be directly mixed with the matrix resin, thereby improving the overall compatibility of the light-converting adhesive film composition. This solution also exhibits excellent compatibility with existing adhesive film systems, thereby addressing the complex and costly preparation process for highly stable light-converting agents.

[0130] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A light-converting adhesive film composition, characterized in that: In parts by weight, the light-converting adhesive film composition comprises: 100 parts of base resin; 0.01 to 10 parts of an organic polymer light conversion agent; 0.01 to 10 parts of additives; The organic polymer light conversion agent is copolymerized by a light conversion agent monomer represented by Formula I and a silane coupling agent containing a carbon-carbon double bond. Wherein, R1 is substituted or unsubstituted C2~C 30 A hydrocarbon group, wherein R1 at least includes a terminal carbon-carbon double bond; R2 and R3 are each independently selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C1~C 30 Alkoxy, substituted or unsubstituted C6~C 30 aryl, substituted or unsubstituted C4~C 30 Any one of heteroaryl, amide, carboxyl, and hydroxyl; n is any integer from 1 to 10; The maximum absorption wavelength of the organic polymer light conversion agent is between 325 and 375 nm, and the maximum emission wavelength is between 400 and 450 nm.

2. The light-converting adhesive film composition according to claim 1, characterized in that: The n is any integer from 1 to 6; And / or, one or more methylene groups in R1, R2 and R3 are independently substituted by -COO-, -O- or -S-; And / or, when R1, R2 and R3 have substituents, the substituents are each independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, -COO-, and nitro.

3. The light conversion adhesive film composition according to claim 1 or 2, characterized in that: The R1 is substituted or unsubstituted C2-C 20 The hydrocarbon group, preferably the R1 is a substituted or unsubstituted C3~C 15 The hydrocarbon group, further, preferably, the terminal carbon-carbon double bond in R1 is a terminal carbon-carbon double bond containing a substituent, and preferably the terminal carbon-carbon double bond containing a substituent is CH2=CH-COO- and / or CH2=C(CH3)-COO-; Preferably, said R1 is selected from Any one of .

4. The light conversion adhesive film composition according to any one of claims 1 to 3, characterized in that: The R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 20 C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 20 aryl, substituted or unsubstituted C4~C 20 Any one of heteroaryl, amide, carboxyl, and hydroxyl; Preferably, the R2 and R3 are each independently selected from substituted or unsubstituted C1 to C 12 C1~C 12 Alkyl, substituted or unsubstituted C1~C 12 Alkoxy, substituted or unsubstituted C6~C 12 aryl, substituted or unsubstituted C4~C 12 Any one of heteroaryl, amide, carboxyl, and hydroxyl; Preferably, the R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 12 C5~C 12 Alkyl, substituted or unsubstituted C5~C 12 Alkoxy, substituted or unsubstituted C6~C 10 aryl, substituted or unsubstituted C4~C 10 Any one of heteroaryl, amide, carboxyl, and hydroxyl; Preferably, the R2 and R3 are each independently selected from substituted or unsubstituted C5 to C 10 C5~C 10 any one of an alkyl group, a substituted or unsubstituted phenyl group; further preferably, the R2 and the R3 are each independently selected from a group in which at least one methylene group of any one of pentyl, hexyl, heptyl, octyl, nonyl and decyl is independently substituted with -COO- or -O-, any one of pentyl, hexyl, heptyl, octyl, nonyl, decyl, amide, carboxyl and hydroxyl.

5. The light-converting adhesive film composition according to claim 1, characterized in that: The structural formula of the light conversion agent monomer is R4 and R5 are each independently selected from H, C1-C 20 C3~C 20 Any one of the alkyl groups; Preferably, the R4 and R5 are independently selected from C1 to C 10 C3~C 10 Any one or more of the alkyl groups, preferably said R4 and said R5 are each independently selected from Any one or more of, wherein "*" represents the connection site of the R4 and the R5 on the benzene ring.

6. The light conversion adhesive film composition according to any one of claims 1 to 5, characterized in that: The molecular weight of the organic polymer light conversion agent is 1000 to 50000 g / mol, preferably 5000 to 40000 g / mol, and further preferably 15000 to 40000 g / mol. The light conversion agent monomer is preferably selected from Any one or more of .

7. The light conversion adhesive film composition according to any one of claims 1 to 6, characterized in that: The silane coupling agent containing a carbon-carbon double bond is selected from any one or more of γ-methacryloxypropyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 5-hexenyltrimethoxysilane, allyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 10-alkenylundecyltrimethoxysilane, vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, acrylamidopropyltrimethoxysilane, allyltriethoxysilane, 11-allyloxyundecyltrimethoxysilane, methacryloxymethyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane.

8. The light conversion adhesive film composition according to any one of claims 1 to 7, characterized in that: The matrix resin is selected from any one or more of EVA, PVA, PMMA, POE, PVB, and silicone; And / or, the auxiliary agent includes any one or more of a hindered amine light stabilizer, an organic peroxide, a cross-linking aid and an adhesive; and / or, the hindered amine light stabilizer is 0.01 to 10 parts by weight; and / or, the organic peroxide is 0.01 to 2 parts by weight; and / or, the cross-linking aid is 0.01 to 3 parts by weight; and / or, the adhesive is 0.01 to 3 parts by weight.

9. A light-converting film, characterized in that: The light-converting adhesive film comprises the light-converting adhesive film composition according to any one of claims 1 to 8.

10. A photovoltaic module comprising a light-converting adhesive film, characterized in that: The light-converting adhesive film is the light-converting adhesive film according to claim 9.

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