N-modified benzotriazole light-converting agent, light-converting adhesive film, and preparation method therefor

Abstract

The present invention relates to the technical field of light-converting adhesive films, and relates in particular to an N-modified benzotriazole light-converting agent, a light-converting adhesive film, and a preparation method therefor. The light-converting agent uses benzotriazole as the parent structure, and one or two aryl or heteroaryl groups are introduced on two sides of the benzene ring; and the benzotriazole is graft-modified at the N-2 position with either a silane or a siloxane. On one hand, the introduction of silane functional groups adjusts the polarity of the light-converting agent to be similar to the polarity of an adhesive film layer, thereby inhibiting migration of the light-converting agent caused by differences in molecular polarity. On the other hand, the introduced Si and Si–O functional groups undergo grafting or hydrolytic condensation reactions during lamination of the adhesive film layer, further suppressing migration of the light-converting agent.

Description

N-modified benzotriazole light-conversion agent, light-conversion adhesive film and preparation method thereof Technical Field

[0001] The present invention belongs to the technical field of light-converting adhesive films, and in particular relates to an N-modified benzotriazole light-converting agent, a light-converting adhesive film and a preparation method thereof. Background Art

[0002] In HJT cell microcrystalline technology, the presence of Si-H bonds will cause the Si-H bonds to open under high-energy ultraviolet light, causing the cell passivation performance to deteriorate and affecting the performance of the module. Therefore, it is necessary to use light conversion materials to absorb ultraviolet light while effectively converting it into visible light to improve the photoelectric conversion efficiency of the module.

[0003] Existing light conversion agents include inorganic light conversion agents and organic light conversion agents. Inorganic light conversion agents have the problem of uneven dispersion, and organic light conversion agents are mostly small molecular structures. Due to the difference in molecular polarity, there are problems such as light conversion agent migration in multi-layer structure films.

[0004] Summary of the Invention

[0005] The present invention provides an N-modified benzotriazole light conversion agent, a light conversion adhesive film and a preparation method thereof, so as to solve the problem that organic light conversion agents are prone to migration.

[0006] In order to solve the above technical problems, the present invention provides an N-modified benzotriazole light-converting agent, comprising: the light-converting agent is based on benzotriazole, and one or both of aryl or heteroaryl groups are introduced on both sides of the benzene ring; and the 2nd position of the N of the benzotriazole is grafted with any one of silane and siloxane; the structural formula of the N-modified benzotriazole light-converting agent is:

[0007] In another aspect, the present invention further provides a method for preparing the aforementioned N-modified benzotriazole light-converting agent, comprising the following steps:

[0008] Step S1,

[0009] Step S2,

[0010] In a third aspect, the present invention further provides a light-converting adhesive film comprising: a base film and the aforementioned N-modified benzotriazole light-converting agent; wherein the N-modified benzotriazole light-converting agent is dispersed in the base film.

[0011] In a fourth aspect, the present invention further provides a method for preparing the aforementioned light-converting adhesive film, comprising: uniformly mixing a base resin, an N-modified benzotriazole light-converting agent, and an auxiliary agent according to a raw material ratio; and casting a film to obtain the light-converting adhesive film.

[0012] In a fifth aspect, the present invention further provides a photovoltaic module, comprising: a front plate, the light-converting adhesive film as described above, a battery cell, an EVA adhesive film, and a back plate arranged in sequence.

[0013] The beneficial effects of the present invention are as follows: the N-position modified benzotriazole light-converting agent, light-converting adhesive film and preparation method thereof use benzotriazole as a matrix, modify the N at position 2 of the triazole, and introduce a C3-C20 alkyl group with a Si or Si-O structure. On the one hand, the introduction of the silane functional group regulates the polarity of the light-converting agent to make it similar to the polarity of the adhesive film layer in which it is located, thereby inhibiting the migration of the light-converting agent due to the difference in molecular polarity; on the other hand, the introduction of the Si or Si-O functional group causes grafting or hydrolysis condensation reaction during the adhesive film lamination process, further inhibiting the migration of the light-converting agent.

[0014] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention.

[0015] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0017] FIG1 is a nuclear magnetic spectrum of 4,7-di-tert-butylphenyl-2-trimethylsilylmethyl-1H-benzotriazole of the present invention. DETAILED DESCRIPTION

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0019] Benzotriazole, as an organic light-converting agent with excellent performance, has been used in light-converting adhesive films. However, due to its small molecular structure, there are differences in molecular polarity in multilayer structural adhesive films, which makes the migration of the light-converting agent very likely to occur.

[0020] The present invention provides an N-modified benzotriazole light-converting agent, comprising: the light-converting agent uses benzotriazole as a matrix, and introduces one or both of an aryl group or a heteroaryl group on both sides of the benzene ring; and the N-2 position of the benzotriazole is graft-modified with any one of silane and siloxane; the structural formula of the N-modified benzotriazole light-converting agent is:

[0021] In this embodiment, specifically, the R0 is -(CH2) n -Si(R a )3, the R a It is a C1-C20 alkyl group or alkoxy group, and n is an integer of 0-5.

[0022] In this embodiment, specifically, R1 is one or two of substituted or unsubstituted aryl, heteroaryl; substituted or unsubstituted thienyl, substituted or unsubstituted amide, and substituted or unsubstituted amino.

[0023] The term "alkyl" refers to and includes both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, more preferably one to six carbon atoms; and include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. In addition, the alkyl group may be optionally substituted.

[0024] The term "alkoxy" refers to: methoxy, ethoxy, propoxy.

[0025] The term "alkenyl" refers to and includes both straight-chain and branched alkenyl groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Preferred alkenyl groups contain from two to fifteen carbon atoms. More preferably, alkenyl groups contain from one to six carbon atoms. In addition, alkenyl groups may be optionally substituted.

[0026] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings can have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred are aryl groups with six carbon atoms, ten carbon atoms or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

[0027] The term "heteroaryl" refers to and encompasses monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have from one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl groups. Heteropolycyclic aromatic ring systems may have from one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, and more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof.

[0028] As used herein, the terms alkyl, alkenyl, aryl, and heteroaryl are independently unsubstituted or substituted with one or more typical substituents.

[0029] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, halogen, nitro, amino, aldehyde, carboxyl, cyano, isocyano.

[0030] In some cases, more preferred general substituents are selected from the group consisting of halogen, nitro, amino, aldehyde, carboxyl, cyano, isocyano, and combinations thereof.

[0031] In other cases, the most preferred general substituents are selected from the group consisting of halogen, nitro, amino, aldehyde, and combinations thereof.

[0032] The term "halogen" refers to: F, Cl, Br, I.

[0033] In another aspect, the present invention further provides a method for preparing the aforementioned N-modified benzotriazole light-converting agent, comprising the following steps:

[0034] Step S1:

[0035] Step S2:

[0036] In this embodiment, specifically, step S1 further includes: selecting acetonitrile as a solvent and adding sodium carbonate for a joint reaction.

[0037] In this embodiment, specifically, step S2 further includes: adding tetrakis(triphenylphosphine)palladium and potassium carbonate to react together, replacing the atmosphere with nitrogen, and then adding a mixed solvent of 1,4-dioxane and water; wherein the volume ratio of 1,4-dioxane to water in the mixed solvent is preferably 5:1.

[0038] In a third aspect, the present invention further provides a light-converting adhesive film comprising: a base film and the aforementioned N-modified benzotriazole light-converting agent; wherein the N-modified benzotriazole light-converting agent is dispersed in the base film.

[0039] In this embodiment, specifically, the raw materials are mixed in proportions by mass: 100 parts of base resin; 0.2 to 1.5 parts of cross-linking agent; 0.1 to 3 parts of auxiliary cross-linking agent; 0.1 to 1 part of light stabilizer; 0.01 to 0.3 parts of antioxidant; 0.2 to 1 part of coupling agent; and 0.01 to 10 parts of N-modified benzotriazole light conversion agent.

[0040] In this embodiment, specifically, the base film includes any one or more combinations of EVA, PMMA, POE, and PVB.

[0041] In this embodiment, specifically, the cross-linking agent includes a combination of one or more of tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0042] In this embodiment, specifically, the auxiliary cross-linking agent includes a combination of one or more of triallyl isocyanurate TAIC and trimethylolpropane triacrylate TMPTA.

[0043] In this embodiment, specifically, the light stabilizer includes a combination of one or more of light stabilizer 622, light stabilizer 770, light stabilizer 944, light stabilizer 783, light stabilizer 123, light stabilizer 765, light stabilizer 2908, light stabilizer 531, light stabilizer 327, and light stabilizer 328.

[0044] In this embodiment, specifically, the antioxidant includes one or more combinations of aromatic amines, hindered phenols, and auxiliary antioxidants.

[0045] In this embodiment, specifically, the coupling agent includes one or more of KH-550, KH-560, KH-570, A-174, KBM-503, Z-6030, KH-792, A-1120, Z-6020, KBM-603, KH-791, A-151, and A-171, or a combination thereof.

[0046] In a fourth aspect, the present invention further provides a method for preparing the aforementioned light-converting adhesive film, comprising: uniformly mixing a base resin, an N-modified benzotriazole light-converting agent, and an auxiliary agent according to a raw material ratio; and casting a film to obtain the light-converting adhesive film.

[0047] In a fifth aspect, the present invention further provides a photovoltaic module, comprising: a front plate, the light-converting adhesive film as described above, a battery cell, an EVA adhesive film, and a back plate arranged in sequence.

[0048] Example

[0049] 4,7-dibromo-1H-benzotriazole (50 mmol, 13.846 g, w = 97%), sodium carbonate (75 mmol, 7.949 g, w = 99%), and iodomethyltrimethylsilane (75 mmol, 16.059 g, w = 97%) were added to a round-bottom flask, and 100 mL of acetonitrile was added as a solvent. The mixture was stirred and heated at 50 degrees Celsius for 2 h. After the reaction was completed, saturated chloride solution was added and the liquids were separated. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. Anhydrous sodium sulfate was added to remove water, filtered, and separated by column to obtain 5.022 g of 2-trimethylsilylmethyl-4,7-dibromo-1H-benzotriazole with an isolation yield of 27.66%.

[0050] The hydrogen spectrum of the intermediate product 2-trimethylsilylmethyl-4,7-dibromo-1H-benzotriazole is 1 H NMR (400MHz, CDCl3) δ7.38(s,2H),4.46(s,2H),0.16(s,9H). 13 C NMR (101MHz, CDCl3) δ143.70,129.14,109.55,49.78,-2.36.

[0051] 2-Trimethylsilylmethyl-4,7-dibromo-1H-benzotriazole (1 mmol, 0.363 g, w = 95%), 4-tert-butylphenylboronic acid (3 mmol, 0.534 g, w = 98%), potassium carbonate (3 mmol, 0.415 g, w = 99%), and tetrakis(triphenylphosphine)palladium (0.1 mmol, 0.415 g, w = 98%) were added to a Schlenk tube. After nitrogen displacement, a mixed solvent of 1,4-dioxane and water (6 mL, volume ratio 5:1) was added. The mixture was stirred and heated at 120 degrees Celsius for 2 h. After the reaction was completed, ethyl acetate and saturated chloride solution were added and extracted to obtain an organic phase. Anhydrous sodium sulfate was added to remove water, filtered, and separated by column to obtain 0.128 g of 4,7-di-tert-butylphenyl-2-trimethylsilylmethyl-1H-benzotriazole with an isolation yield of 27.25%.

[0052] As shown in FIG1 , it is the NMR spectrum of the product of this example.

[0053] The hydrogen spectrum of the obtained product is 1 H NMR (400MHz, CDCl3) δ8.01(d,J=8.4Hz,4H),7.61(s,2H),7.54(d,J=8.4Hz,4H),4.47(s,2H),1.39(s,18H),0.23(s,9H).

[0054] The carbon spectrum of the obtained product is 13 C NMR (101MHz, CDCl3) δ150.84,143.59,134.77,129.47,128.27,125.75,124.07,49.02,34.79,31.51,-2.13.

[0055] The N-modified benzotriazole light-converting agent prepared in the example was further prepared into a light-converting adhesive film according to the following components:

[0056] In this embodiment, specifically, the base EVA resin is preferably DuPont 53071 of the United States, the cross-linking agent is preferably tert-butyl peroxide 2-ethylhexyl carbonate, the auxiliary cross-linking agent is preferably triallyl isocyanurate, the light stabilizer is preferably light stabilizer 770, the antioxidant is preferably hindered phenol antioxidant 1010, and the silane coupling agent is preferably KH-570.

[0057] In this embodiment, specifically, the weight of the films prepared in Examples 1-4 and Comparative Examples 1-4 is 440 g / m2.

[0058] The performance of the light-converting adhesive film prepared in the embodiment was further measured, and the test performance was as follows:

[0059] Test method:

[0060] The film sample (30*30cm) was laminated with the solar cell into a single piece. After baking at 105℃ for 48h, 120h, 192h, and 264h, the distance (unit / cm) of the light conversion agent migration from the front to the back was evaluated.

[0061] In this embodiment, specifically, the R0 substituent in this embodiment is silane. Similarly, methoxysilane can obtain similar effects and solve the same technical problems.

[0062] In summary, the N-position-modified benzotriazole light-converting agent, light-converting adhesive film, and preparation method thereof of the present invention utilize benzotriazole as a matrix, modify the N-position 2 of the triazole, and introduce a C3-C20 alkyl group with a Si or Si-O structure. On the one hand, the introduction of the silane functional group regulates the polarity of the light-converting agent, making it similar to the polarity of the adhesive film layer in which it is located, thereby suppressing the migration of the light-converting agent due to differences in molecular polarity. On the other hand, the introduction of the Si or Si-O functional group causes grafting or hydrolysis-condensation reactions during the adhesive film lamination process, further suppressing the migration of the light-converting agent.

[0063] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. An N-modified benzotriazole light conversion agent, characterized in that: include: The light conversion agent is based on benzotriazole and one or two aromatic or heteroaromatic groups are introduced on both sides of the benzene ring; as well as The 2nd position of N of the benzotriazole is grafted with any one of silane and siloxane; The structural formula of the N-modified benzotriazole light-converting agent is: The R0 is -(CH2) n -Si(R a )3, the R a is a C1-C20 alkyl or alkoxy group, and n is an integer of 0 to 5; The R1 and R2 are one or both of substituted or unsubstituted aryl and heteroaryl groups.

2. A method for preparing the N-modified benzotriazole light-conversion agent according to claim 1, characterized in that: The steps include: Step S1, Step S2, 3. The preparation method according to claim 2, wherein The step S1 further includes: Acetonitrile is selected as solvent and sodium carbonate is added to react together.

4. The preparation method according to claim 2, wherein The step S2 further includes: Tetrakis(triphenylphosphine)palladium and potassium carbonate are added to react together, and after nitrogen replacement, a mixed solvent of 1,4-dioxane and water is added; wherein The volume ratio of 1,4-dioxane to water in the mixed solvent is 5:

1.

5. A light-converting film, characterized in that: include: A base film and the N-modified benzotriazole light conversion agent according to claim 1; in The N-position modified benzotriazole light conversion agent is dispersed in the base film.

6. The light-converting adhesive film according to claim 5, wherein: The raw materials are as follows by mass:

7. A method for preparing the light-converting adhesive film according to claim 6, characterized in that: include: Mix the base resin, N-modified benzotriazole light conversion agent and additives evenly according to the raw material ratio; The light-converting adhesive film is obtained by film casting.

8. A photovoltaic module, characterized in that: include: A front plate, the light-converting adhesive film according to claim 5, a battery cell, an EVA adhesive film, and a back plate are sequentially arranged.

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