CN111454668B - Co-extrusion film, solar cell module and double glazing - Google Patents

Abstract

The invention provides a co-extrusion adhesive film, a solar cell module and double-layer glass. The co-extrusion adhesive film comprises at least two adhesive film layers, wherein the raw materials for forming each adhesive film layer comprise a first component and a second component in parts by weight, the first component is 1-100 parts of first matrix resin grafted with an electron-withdrawing group, the second component independently contains 0.01-25 parts of water producing agent and/or 0.01-2.5 parts of catalyst, each second component is not a water producing agent and is not a catalyst at the same time, the first matrix resin and the water producing agent can generate a crosslinking reaction, and the catalyst can catalyze the crosslinking reaction. When the co-extrusion adhesive film is used as a raw material to prepare the solar cell module, the photoelectric conversion efficiency of the solar cell module can be greatly improved, and the co-extrusion adhesive film is low in cost, simple in process and convenient for industrial popularization.

Description

Co-extruded film, solar cell module and double glazing

technical field

The invention relates to the field of solar cell manufacturing, in particular to a co-extruded adhesive film, a solar cell component and a double-layer glass.

Background technique

In solar modules, the photovoltaic co-extrusion film is the only "barrier" between the silicon wafer and the outer glass. In order to ensure the high photoelectric conversion efficiency of the solar module, the co-extruded film needs to have excellent barrier properties, mechanical properties, resistance to Creep properties, etc., and the above properties of photovoltaic co-extruded films are closely related to their cross-linking degree. In addition, in order to avoid glue overflow during the lamination process, it is necessary to reduce the fluidity of the adhesive film during the lamination process. Generally, the fluidity of the adhesive film is controlled by adjusting the pre-crosslinking degree of the adhesive film.

At present, film cross-linking is generally carried out by the following methods: chemical cross-linking, radiation cross-linking, UV cross-linking and thermal cross-linking. Chemical cross-linking generally involves adding cross-linking agents and co-cross-linking agents to the film. During the lamination process, after the film is heated, the cross-linking agent (such as organic peroxide) decomposes to generate free radicals, which triggers the cross-linking reaction between the matrix resin and the co-cross-linking agent, thereby achieving mechanical properties, thermal resistance and creep resistance. Performance enhancements. However, such a cross-linking system requires a long reaction time, which seriously reduces the manufacturing efficiency of components and increases the manufacturing cost of components. In addition, due to the difference in the linear expansion coefficients of the materials of each layer in the component, a part of the internal stress will be generated. After the package is completed, the temperature of the component will drop to room temperature, and a part of the internal stress will be generated due to the difference in the thermal conductivity of each part. The accumulation of internal stress in the two parts will eventually lead to the occurrence of delamination, blistering, wrinkles and other phenomena between the components, but the residual peroxide in the components will cause the problem of "snail pattern", and will also lead to the welding tape, Corrosion of bus bars or cells. Irradiation crosslinking and UV crosslinking require special equipment, which increases the production cost and makes the process more complicated.

The methods of reducing the fluidity of the adhesive film mainly include the use of low-melting index resin raw materials, irradiation pre-crosslinking treatment, and the like. Among them, the use of low melt index resin will greatly increase the difficulty of film casting and extrusion, greatly increase the production cost, and at the same time reduce the fluidity of the film to a limited extent. Using ultraviolet radiation treatment or electron beam radiation treatment to make the film have a certain degree of pre-crosslinking is the most commonly used treatment method for white high-reflection film, but these methods have high equipment and process costs, and the pre-crosslinking process It will affect the reliability of the film.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a co-extruded adhesive film, a solar cell module and a double-layer glass, so as to solve the problems of easy delamination of the co-extruded adhesive film prepared by the prior art, and long cross-linking time affecting the preparation period.

In order to achieve the above purpose, according to one aspect of the present invention, a co-extruded adhesive film is provided, comprising at least two adhesive film layers, and in parts by weight, the raw materials for forming each adhesive film layer include a first component and a second group The first component is 1-100 parts of the first matrix resin grafted with electron-withdrawing groups, the second components each independently contain 0.01-25 parts of a water-producing agent and/or 0.01-2.5 parts of a catalyst, and each The two components are not simultaneously a water-producing agent and a catalyst, the first matrix resin and the water-producing agent can undergo a cross-linking reaction, and the catalyst can catalyze the cross-linking reaction.

Further, in each of the first base resins grafted with electron-withdrawing groups, the electron-withdrawing groups are independently selected from acid anhydride groups, isocyanate groups, silane coupling groups, acid chloride groups, amino groups, carboxyl groups, hydroxyl groups, mercapto groups, sulfonic acid groups. acid group, epoxy group or cyano group; in the first matrix resin grafted with electron-withdrawing groups, the grafted amount of electron-withdrawing groups is 0.1-10wt%, preferably 0.5-3wt%, more preferably 0.6- 2.8 wt %, more preferably 1 to 2.5 wt %.

Further, the silane coupling group is a free radical obtained by the reaction of an ethylene copolymer with a silane organic compound; preferably, the silane organic compound is selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane Silane, vinyltrimethoxysilane, vinyltriperoxide tert-butylsilane, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris(beta-methoxyethoxy)silane , γ-glycidyl etheroxypropyltrimethoxysilane or γ-methacryloyloxypropyltrimethoxysilane.

Further, the water-producing agent in the raw materials for forming each adhesive film layer is selected from a single compound containing crystal water, a mixture of metal oxides and acids, a mixture of metal hydroxides and acids, and organic compounds containing at least two active groups. One or more of , and each active group is independently selected from amino group, carboxyl group, hydroxyl group, mercapto group or acetal group.

Further, the single compound containing crystal water is selected from calcium disulfate monohydrate, sodium carbonate monohydrate, calcium sulfate dihydrate, copper nitrate trihydrate, copper sulfate pentahydrate, magnesium sulfate hexahydrate, zinc sulfate hexahydrate, sulfuric acid heptahydrate. One or more of zinc, sodium carbonate heptahydrate, ferrous sulfate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulfate decahydrate, sodium carbonate decahydrate and aluminum potassium sulfate dodecahydrate.

Further, the metal oxide is selected from one or more of zinc oxide, tin oxide, calcium oxide, magnesium oxide and aluminum oxide; the metal hydroxide is selected from zinc hydroxide, tin hydroxide, calcium hydroxide, hydroxide One or more of magnesium and aluminum hydroxide; the acid is selected from organic acids, preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, undecanoic acid acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlitic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, behenic acid, behenic acid , wood tar acid, behenic acid, behenic acid, behenic acid, 28 acid, 29 acid, 30 acid, 31 acid, 32 acid, 33 three acid, three One or more of tetradecanoic acid, tripentanoic acid, and trihexanoic acid.

Further, the organic substance containing two or more active groups is selected from 1,3 propylene glycol, 1,3-butanediol, ethylene glycol, ethylenediamine, triethanolamine, tetrahydroxypropylethylenediamine, cis One or more of the group consisting of butenedioic acid, fumaric acid, N,N-dimethylformamide, N-methylol acrylamide, N-hydroxyethyl acrylamide and p-hydroxyphenol.

Further, the catalysts in the raw materials for forming each film layer are independently selected from organic amines, alcohol amine organics, piperazine organics, morpholine organics, bis(2-dimethylaminoethyl) ether, 1, 8 Diazabicyclo[5,4,0]undec-7-ene, pyridine organics, 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine, phenolic organics, carboxylic acids One or more of salts, organic acids, polyols, tin-containing organics, bismuth-containing organics and lead-containing organics.

Further, the organic amine is selected from N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, triethylenediamine, N',N',N',N-tetramethylalkylene diamine, N',N',N',N-pentamethyldiethylenetriamine, triethylamine, N',N-dimethylhexadecamine, N',N-dimethylbutylamine One or more of the group consisting of amine and triethylenediamine; alcohol amine organics are selected from ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N', N-dimethylethanolamine and N, One or more of the group consisting of N'-bis(2hydroxypropyl)aniline; piperazine organic compounds are selected from 1,4-dimethylpiperazine, N',N-diethylpiperazine, N One or more of the group consisting of ',N-diethyl-2-methylpiperazine and N',N-bis-(α-hydroxypropyl)-2-methylpiperazine; morpholines The organic matter is selected from one or more of the group consisting of N-ethylmorpholine, N-methylmorpholine and N-2-hydroxypropyl dimethylmorpholine; the pyridine organic matter is selected from pyridine, N', One or more of the group consisting of N-lutidine, alkylpyridine, halopyridine, aminopyridine, picoline, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine, and dihydropyridine ; Phenolic organic compounds are selected from 2-methylphenol, 1,3-benzenediol, 2,4-xylenol, 2,6-dimethylphenol, 2,4,6-tris(dimethylaminomethyl) ) phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2-(5-chloro-2H-benzotriazol-2-yl )-6-(1,1-dimethylethyl)-4-methylphenol and one or more of the group consisting of methylenebis-benzotriazolyl tetramethylbutylphenol; carboxyl The acid salt is selected from one or more of the group consisting of potassium acetate, zinc acetate, calcium acetate and magnesium acetate; the organic acid is selected from naphthalenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and trimethyl- One or more of the group consisting of N-2-hydroxypropylhexanoic acid; polyol selected from one or more of the group consisting of ethylene glycol, glycerol, trimethylolethane and pentaerythritol ; Tin-containing organics are selected from dibutyltin dilaurate, stannous octoate, dioctyltin dithiolate, dibutyltin oxide, dibutyltin diacetate, dibutyltin bis(dodecyl sulfide) and dibutyl tin laurate maleate one or more of the group consisting of butyltin.

Further, in parts by weight, the raw materials for forming each adhesive film layer also independently include 0-99 parts of the second matrix resin, 0-5 parts of cross-linking agent, 0-5 parts of auxiliary cross-linking agent, 0-1 part of Light stabilizer, 0-2 parts of ultraviolet light absorber, 0-3 parts of tackifier and 0-40 parts of pigment; preferably, in parts by weight, the raw materials for forming each adhesive film layer respectively independently include 1-100 parts First base resin grafted with electron withdrawing groups, 5-90 parts of second base resin, 0.1-2 parts of cross-linking agent, 0.1-3 parts of auxiliary cross-linking agent, 0.1-1 part of light stabilizer, 0.1-1 part of light stabilizer parts of ultraviolet light absorber, 0.1-1 part of tackifier and 0-20 parts of pigment, and 0.1-10 part of water-producing agent and/or 0.05-1 part of catalyst.

Further, the first matrix resin and the second matrix resin in the raw materials for forming each adhesive film layer are independently selected from ethylene copolymers or ethylene-α-olefin copolymers, wherein the ethylene copolymers are ethylene and one or more A copolymer formed from a polymerized monomer selected from vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, butadiene, 1,4-pentadiene, isoprene, ethyl acetate Dicyclopentadiene, dicyclopentadiene, binary or multicomponent copolymers of 1,4-hexadiene, polyvinyl butyral, block copolymers of butadiene/isoprene and styrene, natural Rubber or trans-polyisoprene rubber; ethylene-α-olefin copolymer is obtained by polymerizing ethylene and one or more α-olefins with 3 to 20 carbon atoms, more preferably, the α-olefin is selected from propylene , 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 1 -Octene, 1-decene or 1-dodecene.

Another aspect of the present application also provides a solar cell module, comprising a co-extruded adhesive film, and the co-extruded adhesive film is the co-extruded adhesive film provided by the present application.

Another aspect of the present application also provides a double-layer glass, wherein the double-layer glass includes two glass layers and an adhesive film layer sandwiched between the glass layers, and the adhesive film layer is the co-extruded adhesive film provided by the application.

By applying the technical solution of the present invention, the co-extruded adhesive film does not generate water during extrusion processing, and the temperature during the lamination process is above 120° C. The water-producing agent in the raw materials for forming each adhesive film layer can generate water through physical or chemical reactions. , water can initiate a cross-linking reaction of the first matrix resin grafted with electron-withdrawing groups to form a cross-linked network. At the same time, after each film layer is melted during the application process, the raw materials near the contact surface of the adjacent film layers will penetrate a little. The first matrix resin of the electron group can undergo interlayer crosslinking, or both intralayer crosslinking and interlayer crosslinking. For the above two reasons, the co-extrusion film preparation process does not need to add free radical initiators and bridging agents to achieve the purpose of fast and efficient cross-linking in the application process. The bonding performance is greatly improved, which has the effect of reducing the risk of delamination of the co-extruded film. In addition, limiting the amount of each component in the raw material to a specific range can reduce the fluidity of the co-extruded film during application, control the cross-linking degree of the co-extruded film, and improve its viscosity, mechanical properties and creep resistance. performance and other comprehensive performance. When the solar cell module is prepared by using the above-mentioned co-extruded adhesive film as a raw material, the photoelectric conversion efficiency thereof can be greatly improved, the cost is low, the process is simple, and the industrialization promotion is convenient.

Detailed ways

It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict. The present invention will be described in detail below with reference to the embodiments.

As described in the background art, the co-extruded adhesive film prepared by the prior art has the problems of easy delamination and long cross-linking time, which affects the preparation cycle. In order to solve the above technical problems, the present application provides a co-extruded adhesive film, comprising at least two adhesive film layers, in parts by weight, the raw materials for forming each adhesive film layer include a first component and a second component, wherein the first component One group is composed of 1-100 parts of the first matrix resin grafted with electron withdrawing groups, the second component independently contains 0.01-25 parts of a water-producing agent and/or 0.01-2.5 parts of a catalyst, and the second component does not contain It is a water-producing agent and a catalyst at the same time. The first matrix resin and the water-producing agent can undergo a cross-linking reaction, and the catalyst can catalyze the cross-linking reaction.

The co-extruded film does not produce water during extrusion, and the temperature is above 120°C during the lamination process. The water-producing agent in the raw materials for forming each film layer can produce water through physical or chemical reactions, and water can induce grafting. The first matrix resin of the electron withdrawing group undergoes a cross-linking reaction to form a cross-linked network. At the same time, after each film layer is melted during the application process, under the action of the catalyst, the water-producing agent in the raw material for forming the adjacent film layer and the first matrix resin grafted with electron-withdrawing groups can undergo interlayer cross-linking. Or intralayer crosslinking and interlayer crosslinking. For the above two reasons, the co-extrusion film preparation process does not need to add free radical initiators and bridging agents to achieve the purpose of fast and efficient cross-linking in the application process. The bonding performance is greatly improved, which has the effect of reducing the risk of delamination of the co-extruded film. In addition, limiting the amount of each component in the raw material to a specific range can reduce the fluidity of the co-extruded film during application, control the cross-linking degree of the co-extruded film, and improve its viscosity, mechanical properties and creep resistance. performance and other comprehensive performance.

The pre-crosslinking degree of the co-extruded adhesive film prepared by using the above-mentioned raw materials is 5-70%, and the peeling strength between the co-extruded adhesive film and the glass is greater than 65 N/cm. Therefore, when the solar cell module is prepared by using the above-mentioned co-extruded adhesive film as a raw material, the photoelectric conversion efficiency thereof can be greatly improved, the cost is low, the process is simple, and the industrialization promotion is convenient.

The electron-withdrawing groups grafted on the first matrix resin can improve the degree of cross-linking within each film layer and between adjacent layers, thereby improving the mechanical properties and barrier properties of the co-extruded film. In a preferred embodiment, the electron withdrawing groups in each first matrix resin are independently selected from acid anhydride group, isocyanate group, silane coupling group, acid chloride group, amino group, carboxyl group, hydroxyl group, mercapto group, sulfonic acid group , one or more of epoxy group and cyano group. Compared with other types of electron-withdrawing groups, the above-mentioned electron-withdrawing groups have better cross-linking activity, which is beneficial to further improve the cross-linking degree, mechanical properties and barrier properties of the co-extruded film.

In a preferred embodiment, the silane coupling group is a free radical obtained by reacting an ethylene copolymer with a silane organic compound. The selection of silane coupling groups as electron-withdrawing groups is beneficial to reduce the amount of cross-linking agent and co-cross-linking agent in the formation of co-extruded adhesive film. Make the formula contain less or no polar small molecule additives, which is beneficial to greatly reduce the residue of additives after the co-extrusion film is laminated, and avoid the precipitation of polar small molecule additives during film processing and storage. The adverse effects caused by migration can reduce the problems of air bubbles and snail patterns in the production process of components, and further reduce the production cost of co-extrusion film; at the same time, it can also shorten the lamination time and improve the production efficiency. In order to further improve the reactivity of the electron withdrawing group, more preferably, the above-mentioned silane organic compounds include but are not limited to aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethylsilane. Oxysilane, vinyltripperoxide tert-butylsilane, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris(beta-methoxyethoxy)silane, gamma-glycidyl One or more of etheroxypropyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane.

In order to further improve the cross-linking degree of the co-extruded adhesive film during the application process, and further improve its comprehensive performance, in a preferred embodiment, in the above-mentioned first matrix resin grafted with electron-withdrawing groups, the electron-withdrawing groups are attached The branch amount is 0.1 to 10% by weight, preferably 0.5 to 3%, more preferably 0.6 to 2.8%, further preferably 1 to 2.5%.

The water-producing agent can generate water by a physical or chemical reaction when heated, and then the first matrix resin grafted with electron-withdrawing groups is triggered by water to undergo a cross-linking reaction to form a cross-linked network, thereby improving the overall performance of the co-extruded film. In a preferred embodiment, the water-generating agent in the raw materials for forming each adhesive film layer is selected from a single compound containing crystal water, a mixture of metal oxides and acids, and an organic compound containing at least two active groups. one or more, and each of the reactive groups is independently selected from an amino group, a carboxyl group, a hydroxyl group, a mercapto group or an acetal group.

Due to the high temperature of the co-extrusion film during the application process, the single compound containing crystal water can generate water through physical reactions such as heating during the application process. produce water. In a preferred embodiment, the water producing agent is selected from calcium disulfate monohydrate, sodium carbonate monohydrate, calcium sulfate dihydrate, copper nitrate trihydrate, copper sulfate pentahydrate, magnesium sulfate hexahydrate, zinc sulfate hexahydrate, One or more of zinc sulfate heptahydrate, sodium carbonate heptahydrate, ferrous sulfate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulfate decahydrate, sodium carbonate decahydrate and aluminum potassium sulfate dodecahydrate.

In another preferred embodiment, the water-producing agent is a mixture of metal oxide and acid, or a mixture of metal hydroxide and acid, and the acid is selected from inorganic acid and/or organic acid, metal oxide zinc oxide, One or more of tin oxide, calcium oxide, magnesium oxide and aluminum oxide, and the metal hydroxide is selected from one or more of zinc hydroxide, tin hydroxide, calcium hydroxide, magnesium hydroxide and aluminum hydroxide kind. Acids can release hydrogen ions, so when used with metal oxides or metal hydroxides, acids can produce water through a chemical reaction. In order to further improve the light transmittance of the co-extruded adhesive film, preferably, the above-mentioned metal oxides or metal hydroxides are nano-sized particles. More preferably, the acid is an organic acid, such as saturated and unsaturated fatty acids, preferably saturated fatty acids, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlitic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, behenic acid, 20 Triacid, wood tar acid, behenic acid, behenic acid, behenagoic acid, behenic acid, behenoanic acid, thirty acid, thirty-one acid, behenic acid, thirty-three acid , tristearic acid, tripentaconic acid or trishexadecanoic acid. In order to further improve the compatibility of the above acid with the matrix resin, preferably, the above acid is selected from fatty acids with more than 10 carbon atoms. The stearic fatty acid is more convenient to obtain and the cost is lower.

In another preferred embodiment, the above-mentioned organic substances containing two or more active groups include but are not limited to 1,3-propylene glycol, 1,3-butanediol, ethylene glycol, ethylenediamine, triethanolamine , Tetrahydroxypropyl ethylenediamine, maleic acid, fumaric acid., N,N-dimethylformamide, N-methylol acrylamide, N-hydroxyethyl acrylamide and p-hydroxyphenol one or more of the group. Compared with other water-producing agents, the above-mentioned water-producing agents have better compatibility with other raw materials for forming the co-extrusion film, so that the dispersion of the water-producing agent is more uniform, and the cross-linking effect is better during application, thereby making the water-producing agent more uniform. The performance stability of the co-extruded film is higher.

In a preferred embodiment, the catalysts in the raw materials for forming each adhesive film layer are independently selected from organic amines, alcohol amine organics, piperazine organics, morpholine organics, bis(2-dimethylaminoethyl) base) ether, 1,8 diazabicyclo[5,4,0]undec-7-ene, pyridine organics, 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine, One or more of phenolic organics, carboxylates, organic acids, polyols, tin-containing organics, bismuth-containing organics and lead-containing organics. Compared with other catalysts, the selection of the above catalysts is beneficial to further improve the crosslinking degree of the water-producing agent and the first matrix resin grafted with electron-withdrawing groups, and improve the comprehensive performance of the adhesive film.

More preferably, organic amines include but are not limited to N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, triethylenediamine, N',N',N',N-tetramethyl Alkylenediamine, N',N',N',N-pentamethyldiethylenetriamine, triethylamine, N',N-dimethylbenzylamine, N',N-dimethylamine One or more of the group consisting of hexadecylamine, N',N-dimethylbutylamine and triethylenediamine; alcohol amine organic compounds include but are not limited to ethanolamine, diethanolamine, triethanolamine, triiso One or more of the group consisting of propanolamine, N',N-dimethylethanolamine and N,N'-bis(2-hydroxypropyl)aniline; piperazines include but are not limited to 1,4- Dimethylpiperazine, N',N-diethylpiperazine, N',N-diethyl-2-methylpiperazine and N',N-bis-(α-hydroxypropyl)-2- One or more of the group consisting of methylpiperazine; morpholine organics include but are not limited to N-ethylmorpholine, N-methylmorpholine and N-2-hydroxypropyldimethylmorpholine One or more of the group of pyridines; pyridines include but are not limited to pyridine, N',N-lutidine, alkylpyridine, halopyridine, aminopyridine, picoline, nitropyridine, hydroxypyridine , one or more of the group consisting of benzylpyridine, ethylpyridine and dihydropyridine; phenolic organic compounds are selected from 2-methylphenol, 1,3-benzenediol, 2,4-xylenol, 2,6-dimethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4 -Ethylphenol, 2-(5-Chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol, methylenebis-benzene one or more of the group consisting of triazolyl tetramethylbutylphenol; carboxylate is selected from one or more of the group consisting of potassium acetate, zinc acetate, calcium acetate and magnesium acetate; organic acid One or more selected from the group consisting of naphthalenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and trimethyl-N-2-hydroxypropylhexanoic acid; polyhydric alcohol is selected from ethylene glycol, One or more of the group consisting of glycerol, trimethylolethane and pentaerythritol; tin-containing organic matter is selected from dibutyltin dilaurate, stannous octoate, dioctyltin dithiolate, dibutyltin oxide, One or more of the group consisting of dibutyltin diacetate, dibutyltin bis(dodecyl sulfide), and dibutyltin maleate laurate.

In a preferred embodiment, in parts by weight, the raw materials for forming each adhesive film layer further independently include 0-99 parts of the second matrix resin, 0-5 parts of peroxide-based crosslinking agent, 0-5 parts of Co-crosslinking agent, 0-1 part of light stabilizer, 0-2 parts of ultraviolet light absorber, 0-3 parts of tackifier and 0-40 parts of pigment. More preferably, in parts by weight, the raw materials for forming each of the adhesive film layers independently comprise 1-100 parts of the first matrix resin grafted with electron-withdrawing groups, 5-90 parts of the second matrix Resin, 0.1-2 parts of the cross-linking agent, 0.1-3 parts of the auxiliary cross-linking agent, 0.1-1 part of the light stabilizer, 0.1-1 part of the ultraviolet light absorber, 0.1-1 part of the A tackifier and 0-20 parts of the pigment, and 0.1-10 parts of the water-producing agent and/or 0.05-1 part of the catalyst.

The addition of the second matrix resin is beneficial to improve the mechanical properties and barrier properties of the co-extruded film. The addition of peroxide-based cross-linking agents and co-cross-linking agents is beneficial to further improve the cross-linking performance of the co-extruded film. The addition of UV light absorbers is beneficial to improve the light stability of the co-extruded film, the addition of UV absorbers is beneficial to improve the aging resistance of the co-extruded film, and the addition of tackifiers is beneficial to improve the viscosity of the co-extruded film, and thus has It is beneficial to further reduce the risk of delamination in the subsequent application process, and the addition of pigments can meet the color requirements of users.

In a preferred embodiment, the first matrix resin and the second matrix resin in the raw materials for forming each adhesive film layer are independently selected from ethylene copolymers or ethylene-α-olefin copolymers, wherein the ethylene copolymer is Copolymers of ethylene and one or more polymerizable monomers including but not limited to vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, butadiene, 1,4-pentanediol Ethylene, isoprene, ethylidene norbornene, dicyclopentadiene, binary or multipolymer copolymers of 1,4-hexadiene, polyvinyl butyral, butadiene/isoprene and benzene Block copolymers of ethylene, natural rubber or trans-polyisoprene rubber; ethylene-α-olefin copolymers are obtained by polymerization of ethylene and one or more α-olefins with 3 to 20 carbon atoms, more Preferably, alpha-olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-dodecene. Compared with other matrix resins, selecting the above resins as the first matrix resin or the second matrix resin is beneficial to further improve the comprehensive properties such as the mechanical properties and barrier properties of the co-extruded adhesive film.

The above-mentioned peroxide-based crosslinking agents can be selected from those commonly used in the art. In a preferred embodiment, the peroxide-based cross-linking agents in the raw materials for forming each adhesive film layer are independently selected from tert-butyl isopropyl peroxycarbonate, 2,5-dimethyl-2, 5-(bis-tert-butylperoxy)hexane, 2-ethylhexyl tert-butylperoxycarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethyl ring Hexane, 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis (tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, 2-ethylhexyl peroxide tert-amyl carbonate, 2,5-dimethyl 2,5-dicarbonate One of methyl 2,5-dimethyl 2,5-bis(benzoylperoxy)-hexane, tert-amyl peroxycarbonate and tert-butyl peroxy 3,3,5 trimethylhexanoate one or more.

The above tackifiers can be selected from those commonly used in the art. In a preferred embodiment, the tackifiers in the raw materials for forming each adhesive film layer are independently selected from γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane Silane, γ-(2,3-glycidoxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ- One or more of glycidyl etheroxypropyltrimethylsilane and 3-aminopropyltrimethylsilane. Compared with other tackifiers, the selection of the above-mentioned tackifiers is conducive to further improving the compatibility of each component in the adhesive film layer, thereby further improving the bonding performance of the co-extruded adhesive film.

The co-crosslinking agent can be selected from those commonly used in the art. In order to further improve the cross-linking degree of the co-extruded adhesive film, preferably, the cross-linking assistant in the raw materials for forming each adhesive film layer is independently selected from triallyl isocyanurate, triallyl cyanurate Esters, 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, Bistrimethylolpropane tetraacrylate, Bistrimethylolpropane tetramethacrylate, Pentaerythritol propoxylate 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 - One or more of ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and polyethylene glycol dimethacrylate.

In the above-mentioned raw materials, pigments can be selected from commonly used types in this field, such as hollow glass beads, calcium carbonate, barium sulfate, talc, titanium dioxide, zinc oxide, carbon black, graphene, graphene oxide, copper chrome black, magnesium hydroxide, One or more of aluminum hydroxide, aluminum oxide, magnesium oxide, boron nitride, silicon carbide, ammonium phosphate, ammonium polyphosphate, pentaerythritol, dipentaerythritol, polypentaerythritol ester and melamine polyphosphate borate.

In a preferred embodiment, the light stabilizers in the raw materials for forming each film layer are independently selected from bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid esters , bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, 4-(meth)acryloyloxy-2,2,6,6 - The graft copolymer obtained by the polymerization of tetramethylpiperidine and α-olefin monomers, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 3,5-di-tert-butyl Cetyl-4-hydroxy-benzoate, bis-2,2,6,6-tetramethylpiperidinol, and tris(1,2,2,6,6-pentamethyl-4 - one or more of piperidinyl) phosphites. Compared with other light stabilizers, the selection of the above-mentioned light stabilizers is conducive to further improving the light stability of the co-extruded film, thereby extending its service life.

In a preferred embodiment, the ultraviolet light absorbers in the raw materials for forming each adhesive film layer are independently selected from 2-hydroxy-4-n-octyloxybenzophenone, 2,2-tetramethylene Bis(3,1-benzoxazin-4-one), 2-(2'-hydroxy-5-methylphenyl)benzotriazole and 2,2'-dihydroxy-4,4'-dihydroxy One or more of methoxybenzophenones. Compared with other light stabilizers, the selection of the above-mentioned light stabilizers is beneficial to further improve the aging resistance of the co-extruded film.

Another aspect of the present application further provides a solar cell module, comprising a co-extruded adhesive film, and the co-extruded adhesive film is the co-extruded adhesive film provided by the present application.

The above-mentioned co-extruded adhesive films all have good adhesive properties, barrier properties, mechanical properties, creep resistance, and high stability and reliability, and the co-extruded adhesive films also have the advantage of being difficult to delaminate. Therefore, the solar cell module containing the above-mentioned co-extruded adhesive film has high photoelectric conversion efficiency, low cost, simple process, and is convenient for industrialization.

Another aspect of the present application also provides a double-layer glass, comprising two glass layers and an adhesive film layer sandwiched between the glass layers, wherein the adhesive film layer is the co-extruded adhesive film provided by the application.

The above-mentioned co-extruded adhesive films all have good adhesive properties, barrier properties, mechanical properties, creep resistance, and high stability and reliability, and the co-extruded adhesive films also have the advantage of being difficult to delaminate. Therefore, the double-layer glass containing the above-mentioned co-extruded adhesive film has good lamination properties, good barrier properties and mechanical properties, low cost, simple process, and is convenient for industrialization.

The present application will be described in further detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present application.

Example 1

The raw material of the first adhesive film layer: in parts by weight, take 30 parts of matrix resin ethylene-vinyl acetate copolymer (the VA content is 28wt%, DuPont, USA), 70 parts of vinyltrimethoxysilane grafted ethylene-acetic acid Vinyl ester copolymer (28wt% VA content, 2wt% graft rate, DuPont, USA), 1.5 parts of catalyst N,N-dimethylbenzylamine, 0.8 part of crosslinking agent 2,5-dimethyl-2, 5-bis(tert-butylperoxy)hexane, 0.8 part of co-crosslinking agent trimethylolpropane trimethacrylate.

The raw material of the second adhesive film layer: in parts by weight, take 10 parts of matrix resin ethylene-hexene copolymer (Dow, USA), 80 parts of vinyltrimethoxysilane-grafted ethylene-hexene copolymer (grafted ethylene-hexene copolymer). rate 2wt%, Dow, USA), 10 parts of water-producing agent calcium disulfate monohydrate masterbatch, and 10 parts of water-producing agent 1,3-propanediol. Wherein, the calcium sulfate monohydrate master batch is obtained by granulation of calcium disulfate monohydrate and ethylene-hexene copolymer through a twin-screw extruder, and relative to 100 parts of ethylene-octene copolymer, the consumption of calcium sulfate monohydrate is 20 share.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The double-layer composite photovoltaic co-extrusion film is prepared by the processes of film forming, cooling, slitting and winding, which is recorded as E1. The thickness of the second film layer is 0.2mm and the thickness of the first film layer is 0.3mm through the calculation of the distributor. .

Example 2

Raw materials of the first adhesive film layer: in parts by weight, take 100 parts of ethylene-octene copolymers grafted with isocyanate groups (grafting rate 3wt%, Dow, USA), 1 part of catalyst ethylene glycol, 0.01 part of catalyst Stannous octoate, 2 parts crosslinker 1,1-bis(tert-amylperoxy)cyclohexane, 0.02 part co-crosslinker trimethylolpropane triacrylate, 1.0 part co-crosslinker ethoxylated triglyceride Acrylate 0.8 part tackifier vinyl triperoxide tert-butyl silane, 0.8 part light stabilizer sebacic acid bis-2,2,6,6-tetramethylpiperidinol, 20 parts titanium dioxide.

Raw materials of the second adhesive film layer: in parts by weight, take 100 parts of ethylene-octene copolymers grafted with isocyanate groups (grafting rate 3wt%, Dow, USA), 5 parts of water-producing agents (calcium oxide and lauric acid) acid masterbatch), 20 parts of water-producing agent 1,4-butanediol. Among them, the master batch of calcium oxide and lauric acid is obtained by granulation of calcium oxide, lauric acid and ethylene-octene copolymer (Dow, USA) through twin-screw extruder. Relative to 100 parts of ethylene-octene copolymer, the oxidation Calcium is 3 parts and lauric acid is 10 parts.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The first film layer, the second film layer and the first film layer three-layer composite photovoltaic co-extruded film are prepared by the processes of film forming, cooling, slitting and winding, which are recorded as E2. The thickness of the second film layer is 0.1mm, the thickness of the first film layer is 0.2mm, and the total thickness of the film is 0.5mm.

Example 3

Raw materials of the first adhesive film layer: in parts by weight, 50 parts of matrix resin ethylene-propylene copolymer (Dow, USA), 50 parts of ethylene-propylene copolymer containing 1.0% acid anhydride (Dow, USA), 2.5 parts of catalyst Sanya Ethyldiamine, 0.5 part crosslinker isopropyl tert-butyl peroxycarbonate, 0.9 part co-crosslinker triallyl isocyanurate, 0.5 part tackifier vinyltriethoxysilane, 0.02 parts of the light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester.

Raw materials of the second adhesive film layer: in parts by weight, take 20 parts of ethylene-propylene copolymer containing 1.0% acid anhydride (Dow, USA), and 80 parts of ethylene-pentene copolymer containing 1.2% mercapto group (Dow, USA) , 0.5 parts of catalyst N,N-dimethylcyclohexylamine, 2 parts of first crosslinking agent 1,1-bis(tert-amylperoxy)cyclohexane, 0.02 parts of auxiliary crosslinking agent trimethylolpropane trimethylolide Acrylates, 0.8 parts First Crosslinker Vinyl Triperoxide tert-Butyl Silane, 0.8 Parts Light Stabilizer Bis-2,2,6,6-Tetramethylpiperidinol Sebacate, 2 Parts Tackifier γ-(2,3-glycidoxy)propyltrimethoxysilane.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The first film layer, the second film layer, the first film layer, and the second film layer four-layer composite photovoltaic co-extrusion film are prepared by the processes of film forming, cooling, slitting and winding, which are denoted as E3, According to the calculation of the distributor, the thickness of the second film layer of the co-extruded film is 0.1 mm, the thickness of the first film layer is 0.1 mm, and the total thickness of the film is 0.4 mm.

Example 4

Raw materials of the first adhesive film layer: 20 parts of matrix resin ethylene-butene copolymer (Dow, USA), 30 parts of ethylene-pentene copolymer containing 4.0% silane coupling group, 50 parts of ethylene containing 1.5% hydroxyl group -Pentene copolymer (Dow, USA), 1 part of catalyst trimethyl-N-2-hydroxypropylhexanoic acid, 2 parts of cross-linking agent tert-butyl peroxycarbonate-2-ethylhexyl ester, 1 part of auxiliary Crosslinking agent diethylene glycol dimethacrylate, 0.8 parts light stabilizer tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite, 40 parts pigment carbon black.

Raw materials of the second adhesive film layer: in parts by weight, take 20 parts of ethylene-propylene copolymer (Dow, USA), 80 parts of ethylene-pentene copolymer (Dow, USA) containing 1.5% hydroxyl group, and 0.5 part of produced water ethylene glycol, 0.5 parts catalyst N',N-dimethylhexadecylamine, 2 parts co-crosslinking agent ethyl tert-butyl peroxyisopropyl carbonate, 1 part co-crosslinking agent diethylene glycol dimethyl Acrylate, 0.8 part light stabilizer tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The first adhesive film layer, the second adhesive film layer, the first adhesive film layer, the second adhesive film layer, the first adhesive film layer five-layer composite photovoltaic co-extruded adhesive are prepared by the processes of film forming, cooling, slitting and winding. The film, denoted as E4, is calculated by the distributor to know that the thickness of the second film layer of the co-extruded film is 0.2mm, the thickness of the first film layer is 0.1mm, and the total thickness of the film is 0.7mm.

Example 5

Raw materials of the first adhesive film layer: 10 parts of base resin ethylene-methyl methacrylate copolymer (Dow DuPont, USA), 35 parts of ethylene-pentene copolymer containing 2.5% silane coupling group (Dow, USA) , 35 parts of ethylene-octene copolymer containing 6.5% sulfonic acid group (Dow, USA), 20 parts of ethylene-butene copolymer (Dow, USA) containing 2.5% isocyanate group, 0.3 part of catalyst N', N',N',N-pentamethyldiethylenetriamine, 0.5 part co-crosslinker 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, 0.9 Parts of light stabilizer bis-2,2,6,6-tetramethylpiperidinol sebacic acid, 3 parts of pigment titanium dioxide and 2 parts of pigment hollow glass beads

Raw materials of the second adhesive film layer: in parts by weight, 10 parts of ethylene-methyl methacrylate copolymer (DuPont, USA), 35 parts of ethylene-pentene copolymer containing 2.5% silane coupling group (Dow, USA) ), 35 parts of ethylene-octene copolymer containing 6.5% sulfonic acid group (Dow, USA), 20 parts of masterbatch containing zinc oxide and stearic acid. Wherein, the master batch containing zinc oxide and stearic acid is obtained by granulating zinc oxide, stearic acid and ethylene-octene copolymer through twin-screw extruder. Relative to 100 parts of ethylene-octene copolymer, calcium oxide is 2 parts and 7 parts lauric acid. Add 0.1 part of 2,2-bis(tert-butylperoxy)butane, 1 part of trimethylolpropane trimethacrylate, 0.8 part of bis(1-octyloxy-2,2,6,6-tetra Methyl-4-piperidinyl) sebate, 0.8 parts of 2-(2'-hydroxy-5-methylphenyl)benzotriazole.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The first film layer and the second film layer two-layer composite photovoltaic co-extrusion film are prepared by the processes of film forming, cooling, slitting and winding, which are recorded as E5. The second film of the co-extruded film can be known through the calculation of the distributor. The thickness of the film layer is 0.2mm, the thickness of the first film layer is 0.25mm, and the total thickness of the film is 0.45mm.

Example 6

Raw materials of the first adhesive film layer: 100 parts of ethylene-pentene copolymer (Dow, USA) containing 2.0% of silane coupling group and 2.5% of acid chloride group, 0.4 part of catalyst triethylenediamine, 1.0 part of cross-linked Linking agent 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1.0 part of co-crosslinking agent diethylene glycol dimethacrylate, 0.05 part of light stabilizer bis (1-Octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, 0.8 part second UV absorber 2,2'-dihydroxy-4,4' -Dimethoxybenzophenone.

Raw materials of the second adhesive film layer: by weight, 55 parts of ethylene-pentene copolymer containing 3.5% silane coupling group (Dow, USA), 45 parts of ethylene-octene copolymer containing 3.5% isocyanate group (Dow, USA), 1.0 part of water-producing agent 1,4-butanediol, 0.5 part of water-producing agent ethylenediamine containing 2.5% amino group, 0.5 part of water-producing agent triethanolamine, 1.0 part of cross-linking agent 1,1- Bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1.0 part of co-crosslinker diethylene glycol dimethacrylate, 0.5 part of light stabilizer 3,5-di-tert-butyl Cetyl-4-hydroxy-benzoate, 0.8 parts of the second UV absorber 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The first film layer and the second film layer two-layer composite photovoltaic co-extrusion film are prepared by the processes of film forming, cooling, slitting and winding, which are recorded as E6. The second glue of the co-extruded film can be known through the calculation of the distributor. The thickness of the film layer is 0.2mm, the thickness of the first film layer is 0.25mm, and the total thickness of the film is 0.45mm.

Example 7

The difference from Example 1 is that,

The raw material of the first adhesive film layer: in parts by weight, take 100 parts of a matrix resin (ethylene-vinyl acetate copolymer grafted with vinyltrimethoxysilane grafted with an electron-withdrawing group, the VA content is 28wt%, the Branch rate 2wt%, DuPont) and 0.01 part of catalyst (N,N-dimethylbenzylamine);

The raw material of the second adhesive film layer: in parts by weight, take 1 part of the base resin (ethylene-hexene copolymer grafted with vinyltrimethoxysilane grafted with an electron-withdrawing group, the graft ratio is 2wt%, the American ceramics ) and 25 parts of a water-producing agent (calcium disulfate monohydrate and 1,3-propanediol in a weight ratio of 1:1).

Example 8

The difference from Example 1 is that,

The raw material of the first adhesive film layer: in parts by weight, take 1 part of the base resin (ethylene-vinyl acetate copolymer grafted with vinyltrimethoxysilane, the VA content is 28wt%, the base resin grafted with electron-withdrawing group) Branch rate 2wt%, DuPont) and 2.5 parts of catalyst (N,N-dimethylbenzylamine);

The raw material of the second adhesive film layer: in parts by weight, take 100 parts of the base resin (ethylene-hexene copolymer grafted with vinyltrimethoxysilane grafted with an electron-withdrawing group, the graft ratio is 2wt%, the American ceramics ®) and 0.01 part of a water-producing agent (calcium disulfate monohydrate and 1,3-propanediol in a weight ratio of 1:1).

Example 9

The difference from Example 1 is that,

The raw material of the first adhesive film layer: in parts by weight, take 100 parts of a matrix resin (ethylene-vinyl acetate copolymer grafted with vinyltrimethoxysilane grafted with an electron-withdrawing group, the VA content is 28wt%, the The branch rate was 2wt%, DuPont, USA), 1.5 parts of catalyst N,N-methylbenzylamine, 0.8 parts of crosslinking agent 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane were added, 0.8 part of co-crosslinking agent trimethylolpropane trimethacrylate.

The raw material of the second adhesive film layer: in parts by weight, take 100 parts of the base resin (ethylene-hexene copolymer grafted with vinyltrimethoxysilane grafted with an electron-withdrawing group, the graft ratio is 2wt%, the American ceramics ), 10 parts of the masterbatch of calcium disulfate monohydrate as water-producing agent, and 10 parts of water-producing agent 1,3-propanediol. Wherein, the master batch of calcium sulfate monohydrate is obtained by granulation of calcium disulfate monohydrate and ethylene-hexene copolymer through twin-screw extruder, and relative to 100 parts of ethylene-octene copolymer, the consumption of calcium oxalate monohydrate is 20 servings.

Example 10

The difference from Example 1 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all ethylene-vinyl acetate copolymers grafted with isocyanate groups (the VA content is 28 wt %, and the grafting rate is 2 wt %). , DuPont USA).

Example 11

The difference from Example 1 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all ethylene-vinyl acetate copolymers grafted with acid chloride groups (the VA content is 28 wt %, and the grafting rate is 2 wt %). , DuPont USA).

Example 12

The difference from Example 1 is that,

The base resins grafted with electron-absorbing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all amino-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt %, the grafting rate is 2 wt %, DuPont USA).

Example 13

The difference from Example 1 is that,

The matrix resins grafted with electron-absorbing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all carboxyl-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt %, and the grafting rate is 2 wt %, DuPont USA).

Example 14

The difference from Example 1 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all sulfonic acid group-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt %, and the graft ratio is 2 wt %). %, DuPont USA).

Example 15

The difference from Example 1 is that,

The matrix resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all epoxy group-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt %, and the graft ratio is 2 wt %). %, DuPont USA).

Example 16

The difference from Example 1 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all cyano group-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt %, and the graft ratio is 2 wt %). , DuPont USA).

Example 17

The difference from Example 16 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all cyano group-grafted ethylene-vinyl acetate copolymers (the VA content is 28wt%, and the graft ratio is 0.8wt%). %, DuPont USA).

Example 18

The difference from Example 16 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all cyano group-grafted ethylene-vinyl acetate copolymers (the VA content is 28wt%, and the graft ratio is 0.1wt%). %, DuPont USA).

Example 19

The difference from Example 16 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all cyano group-grafted ethylene-vinyl acetate copolymers (the VA content is 28 wt%, and the graft ratio is 10 wt%. , DuPont USA).

Example 20

The difference from Example 16 is that,

The base resins grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer are all cyano group-grafted ethylene-vinyl acetate copolymers (the VA content is 28wt%, and the graft ratio is 0.05wt%). %, DuPont USA).

Example 21

The difference from Example 1 is that the catalyst is 1,8 diazabicyclo[5,4,0]undec-7-ene.

Example 22

The difference from Example 1 is that the catalyst is 1,4-dimethylpiperazine.

Example 23

The difference from Example 1 is that the catalyst is N,N-dimethylcyclohexylamine.

Example 24

The difference from Example 1 is that the catalyst is bis(2-dimethylaminoethyl) ether.

Example 25

The difference from Example 1 is that the catalyst is N-methylmorpholine.

Example 26

The difference with Example 1 is that the catalyst is N', N-lutidine

Example 27

The difference from Example 1 is that the catalyst is ethylene glycol.

Example 28

The difference from Example 1 is that 2 parts of tackifier (γ-aminopropyltriethoxysilane) are added to the raw material of the first adhesive film layer.

Example 29

The difference from Example 28 is that the tackifier is γ-methacryloyloxypropyltrimethoxysilane.

Example 30

The difference from Example 28 is that the tackifier is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Example 31

The difference from Example 1 is that,

The first adhesive film layer: in parts by weight, take 30 parts of matrix resin ethylene-vinyl acetate copolymer (the VA content is 28wt%, DuPont, USA), 70 parts of vinyltrimethoxysilane grafted ethylene-vinyl acetate Copolymer (28wt% VA content, 2wt% graft rate, DuPont, USA), 1.5 parts of catalyst N,N-methylbenzylamine, 10 parts of water-producing agent calcium disulfate monohydrate, 0.8 parts of cross-linking agent 2, 5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 0.8 parts of co-crosslinking agent trimethylolpropane trimethacrylate.

Second adhesive film layer: in parts by weight, take 10 parts of matrix resin ethylene-hexene copolymer (Dow, USA), 80 parts of vinyltrimethoxysilane grafted ethylene-hexene copolymer (graft ratio 2wt %, Dow, USA), 10 parts of water-producing agent calcium disulfate monohydrate, 10 parts of water-producing agent 1,3-propanediol. Wherein, the master batch of calcium sulfate monohydrate is obtained by granulation of calcium disulfate monohydrate and ethylene-hexene copolymer through twin-screw extruder, and relative to 100 parts of ethylene-octene copolymer, the consumption of calcium oxalate monohydrate is 20 servings.

Comparative Example 1

The raw material of the first adhesive film layer: in parts by weight, take 30 parts of matrix resin ethylene-vinyl acetate copolymer (the VA content is 28wt%, DuPont, USA), 70 parts of vinyltrimethoxysilane grafted ethylene-acetic acid Vinyl ester copolymer (28wt% VA content, 2wt% graft rate, DuPont, USA), 0.8 part of crosslinking agent 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane was added, 0.8 part of co-crosslinking agent trimethylolpropane trimethacrylate.

The raw material of the second adhesive film layer: in parts by weight, take 10 parts of matrix resin ethylene-hexene copolymer (Dow, USA), 80 parts of vinyltrimethoxysilane-grafted ethylene-hexene copolymer (grafted ethylene-hexene copolymer). rate 2wt%, Dow, USA).

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted and extruded, and then flows into the same die. The double-layer composite photovoltaic co-extrusion film is prepared by the processes of film forming, cooling, slitting and winding, which is recorded as R1. The thickness of the second film layer is 0.2mm and the thickness of the first film layer is 0.3mm through the calculation of the distributor. .

Comparative Example 2

The first adhesive film layer: in parts by weight, take 100 parts of matrix resin ethylene-pentene copolymer (Dow, USA), 1.0 part of cross-linking agent 1,1-bis(tert-amylperoxy)-3,3 ,5-trimethylcyclohexane, 1.0 part of co-crosslinking agent diethylene glycol dimethacrylate, 0.05 part of light stabilizer bis(1-octyloxy-2,2,6,6-tetramethyl) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 0.8 part of UV absorber.

Second adhesive film layer: in parts by weight, take 100 parts of matrix resin ethylene-octene copolymer (Dow, USA), 1.0 part of 1,1-bis(tert-amylperoxy)-3,3,5- Trimethylcyclohexane, 1.0 part of diethylene glycol dimethacrylate, 0.5 part of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, 0.8 part of 2,2'- Dihydroxy-4,4'-dimethoxybenzophenone.

After the above-mentioned raw materials of the first adhesive film layer and the raw materials of the second adhesive film layer are respectively mixed, they are added to different extruders. The extruded material of the first adhesive film layer and the extruded material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die, and merged in the T die to form a melt stream, which is melted, extruded, and flowed. The first film layer and the second film layer two-layer composite photovoltaic co-extruded film are prepared by the processes of film forming, cooling, slitting and winding, which are recorded as R2. The second film of the co-extruded film can be known through the calculation of the distributor. The thickness of the film layer is 0.2mm, the thickness of the first film layer is 0.25mm, and the total thickness of the film is 0.45mm.

Comparative Example 3

The difference from Example 1 is that the consumption of the water-producing agent is 30 parts, and the consumption of the catalyst is 3 parts.

The examples and the comparative examples are tested for adhesion and cross-linking degree, and the lamination characteristics and reliability of the components are compared.

Test items and test methods

1. Adhesion

According to 300mm×150mm glass/adhesive film (two layers)/flexible backsheet, stack them in sequence and put them in a vacuum laminator, and press them according to the lamination process of 150C and 18 minutes to make a pressed part.

Cut the flexible backsheet/film into 10mm±0.5mm samples every 5mm in the width direction to test the adhesion between the film and the glass. According to the test method of GB/T 2790-1995, test the peeling force between the film and the glass on a tensile testing machine at a tensile speed of 100mm/min±10mm/min, and take the arithmetic mean of the three tests, accurate to 0.1 N/cm.

2. Degree of cross-linking

Tested by heating extraction with xylene. The ratio of the mass undissolved in xylene to the initial mass refers to the degree of crosslinking. Take the arithmetic mean of three samples, in %.

3. Appearance evaluation of component lamination

Laminate according to the lamination sequence of glass/film/cell/film/glass, and lamination according to the lamination process of the above adhesive force test to make a standard double-glass solar cell module, the specification of which is 60 pieces ( 6×10) version of the battery sheet. According to different films, 100 modules were produced for appearance evaluation. The evaluation criteria are based on the occurrence of bubbles, impurities, and delamination between the film and the battery or glass, as follows:

○: None △: Slight ×: Severe

4. Component snail pattern test:

The adhesive film is laminated with the battery, backplane (WVTR<2.0), coated glass, junction box and other materials to make 4 small battery module samples.

After the module sample was fabricated, the battery was cracked, placed at 85°C, 85% RH, and energized for 8A for 168h; after taking it out, the positive and negative electrodes of the sample junction box were short-circuited, and the light was 10kWh/m ² , which was regarded as a cycle, continuous Do 3 cycles. Before and after each cycle, visually inspect the appearance of the samples to observe whether there are snail patterns on the surface of each cell.

The evaluation results are shown in Table 1 below.

Table 1

Comparing Examples 1 to 31 and Comparative Examples 1 to 3, it can be seen that the adhesive film of the present invention has good adhesion to glass after lamination, and maintains good reliability, and its performance in terms of component appearance and snail pattern Significantly better than the comparative film and its prepared assembly.

Comparing Examples 1, 7 to 8 and Comparative Example 3, it can be seen that limiting the amount of the water-producing agent to be within the preferred range of the present application is conducive to improving the performance of the co-extrusion packaging film.

Comparing Examples 1, 9 to 20, it can be seen that the selection of the preferred matrix resin grafted with electron-withdrawing groups in the present application is beneficial to improve the performance of the co-extruded encapsulation film.

Comparing Examples 1, 21 to 27, it can be seen that the selection of the catalyst preferred in the present application is beneficial to improve the performance of the co-extrusion packaging film.

Comparing Examples 1, 28 to 30, it can be seen that adding a tackifier and selecting the preferred tackifier in this application is beneficial to improve the performance of the co-extrusion packaging film.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (17)

1. a co-extruded adhesive film, is characterized in that, comprises at least two adhesive film layers, by weight, the raw material that forms each described adhesive film layer comprises first component and second component, described first The components are 1-100 parts of the first matrix resin grafted with electron withdrawing groups, the second components each independently contain 0.01-25 parts of a water-producing agent and/or 0.01-2.5 parts of a catalyst, and each of the first The two components are not both the water-producing agent and the catalyst at the same time, the first matrix resin and the water-producing agent can undergo a cross-linking reaction, and the catalyst can catalyze the cross-linking reaction; The water-producing agent in the raw materials for forming each of the adhesive film layers is selected from organic substances containing at least two active groups, and one or more of the following compounds containing a single compound containing crystal water, a mixture of metal oxides and acids , a mixture of metal hydroxide and acid, and each of the reactive groups is independently selected from amino, carboxyl, hydroxyl, mercapto or acetal; The catalysts in the raw materials for forming each of the adhesive film layers are independently selected from organic amines, alcohol amine organic compounds, piperazine organic compounds, morpholine organic compounds, bis(2-dimethylaminoethyl) ether, 1,8 Diazabicyclo[5,4,0]undec-7-ene, pyridine organics, 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine, phenolic organics, carboxylates , one or more of organic acids, polyols, bismuth-containing organics and lead-containing organics; In each of the first base resins grafted with electron-withdrawing groups, the electron-withdrawing groups are independently selected from acid anhydride groups, isocyanate groups, silane coupling groups, acid chloride groups, amino groups, carboxyl groups, hydroxyl groups, mercapto groups, sulfonic acid group, epoxy group or cyano group; In the first base resin grafted with electron-withdrawing groups, the grafted amount of the electron-withdrawing groups is 0.1-10 wt %. 2 . The co-extruded adhesive film according to claim 1 , wherein, in the first matrix resin grafted with electron-withdrawing groups, the grafted amount of the electron-withdrawing groups is 0.5-3 wt %. 3 . . 3. The co-extruded adhesive film according to claim 2, wherein in the first matrix resin grafted with electron-withdrawing groups, the graft amount of the electron-withdrawing groups is 0.6-2.8 wt % . 4. The co-extruded adhesive film according to claim 3, wherein in the first base resin grafted with electron-withdrawing groups, the graft amount of the electron-withdrawing groups is 1-2.5 wt % . 5 . The co-extruded adhesive film according to claim 2 , wherein the silane coupling group is a free radical obtained by reacting an ethylene copolymer with a silane organic compound. 6 . 6 . The co-extruded adhesive film according to claim 5 , wherein the organic silane is selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyl trimethoxysilane, vinyltriperoxide tert-butylsilane, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris(beta-methoxyethoxy)silane, gamma- Glycidyl etheroxypropyltrimethoxysilane or gamma-methacryloyloxypropyltrimethoxysilane. 7. The co-extrusion film according to claim 1, wherein the single compound containing crystal water is selected from the group consisting of calcium disulfate monohydrate, sodium carbonate monohydrate, calcium sulfate dihydrate, copper nitrate trihydrate, pentahydrate Copper sulfate hydrate, magnesium sulfate hexahydrate, zinc sulfate hexahydrate, zinc sulfate heptahydrate, sodium carbonate heptahydrate, ferrous sulfate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulfate decahydrate, sodium carbonate decahydrate and One or more of aluminum potassium sulfate dodecahydrate. 8. The co-extruded adhesive film according to claim 1, wherein the metal oxide is selected from one or more of zinc oxide, tin oxide, calcium oxide, magnesium oxide and aluminum oxide; The metal hydroxide is selected from one or more of zinc hydroxide, tin hydroxide, calcium hydroxide, magnesium hydroxide and aluminum hydroxide; The acids are each independently selected from organic acids. 9. The co-extrusion film according to claim 8, wherein the organic acid is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlitic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, behenic acid, 20 Triacid, wood tar acid, behenic acid, behenic acid, behenagoic acid, behenic acid, behenoanic acid, thirty acid, thirty-one acid, behenic acid, thirty-three acid , one or more of tristearic acid, tripentanoic acid and trishexanoic acid. 10. The co-extrusion film according to claim 1, wherein the organic substance containing two or more active groups is selected from the group consisting of 1,3 propylene glycol, 1,3-butanediol, ethylene glycol , ethylenediamine, triethanolamine, tetrahydroxypropylethylenediamine, maleic acid, fumaric acid, N-methylol acrylamide, N-hydroxyethyl acrylamide and p-hydroxyphenol in the group consisting of one or more. 11. The co-extrusion film according to claim 1, wherein the organic amine is selected from the group consisting of N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, triethylenediamine , N',N',N',N-tetramethylalkylenediamine, N',N',N',N-pentamethyldiethylenetriamine, triethylamine, N',N - one or more of the group consisting of dimethylhexadecamine, N',N-dimethylbutylamine and triethylenediamine; The alcoholamine organic matter is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N',N-dimethylethanolamine and N,N'-bis(2hydroxypropyl)aniline. one or more; The piperazine organic matter is selected from 1,4-dimethylpiperazine, N',N-diethylpiperazine, N',N-diethyl-2-methylpiperazine and N',N- One or more of the group consisting of bis-(α-hydroxypropyl)-2-methylpiperazine; The morpholine organic matter is selected from one or more of the group consisting of N-ethylmorpholine, N-methylmorpholine and N-2-hydroxypropyldimethylmorpholine; The pyridine organic matter is selected from pyridine, N',N-lutidine, alkylpyridine, halopyridine, aminopyridine, picoline, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine, dipyridine one or more of the group consisting of hydrogen pyridine; The phenolic organic matter is selected from 2-methylphenol, 1,3-benzenediol, 2,4-xylenol, 2,6-dimethylphenol, 2,4,6-tris(dimethylaminomethane) base)phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2-(5-chloro-2H-benzotriazole-2- one or more of the group consisting of)-6-(1,1-dimethylethyl)-4-methylphenol and methylenebis-benzotriazolyltetramethylbutylphenol; The carboxylate is selected from one or more of the group consisting of potassium acetate, zinc acetate, calcium acetate and magnesium acetate; The organic acid is selected from one or more of the group consisting of naphthalenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and trimethyl-N-2-hydroxypropylhexanoic acid; The polyol is selected from one or more of the group consisting of ethylene glycol, glycerol, trimethylolethane and pentaerythritol. 12. The co-extruded adhesive film according to any one of claims 1 to 4, wherein, in parts by weight, the raw materials for forming each adhesive film layer further independently comprise 0-99 parts of the second matrix Resin, 0-5 parts of cross-linking agent, 0-5 parts of auxiliary cross-linking agent, 0-1 part of light stabilizer, 0-2 parts of ultraviolet light absorber, 0-3 parts of tackifier and 0-40 parts of pigment. 13. The co-extruded adhesive film according to claim 12, wherein, in parts by weight, the raw materials for forming each of the adhesive film layers independently comprise 1-100 parts of the grafted electron-withdrawing group. The first matrix resin, 5-90 parts of the second matrix resin, 0.1-2 parts of the cross-linking agent, 0.1-3 parts of the auxiliary cross-linking agent, 0.1-1 part of the light stabilizer, 0.1-1 part parts of the ultraviolet light absorber, 0.1-1 part of the tackifier, 0-20 parts of the pigment, and 0.1-10 parts of the water-producing agent and/or 0.05-1 part of the catalyst. 14. The co-extruded adhesive film according to claim 12, wherein the first matrix resin and the second matrix resin in the raw materials for forming each of the adhesive film layers are independently selected from ethylene copolymers or ethylene-α - Olefin copolymers, Wherein, the ethylene copolymer is a copolymer formed by ethylene and one or more polymerized monomers selected from vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, butanediol Dicyclopentadiene, 1,4-pentadiene, isoprene, ethylidene norbornene, dicyclopentadiene, binary or multipolymer copolymers of 1,4-hexadiene, polyvinyl butyral, butadiene Block copolymers of ene/isoprene and styrene, natural rubber or trans-polyisoprene rubber; The ethylene-α-olefin copolymer is obtained by polymerizing ethylene and one or more α-olefins with 3-20 carbon atoms. 15. The co-extruded adhesive film according to claim 14, wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene ene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-dodecene. 16 . A solar cell module comprising a co-extruded adhesive film, wherein the co-extruded adhesive film is the co-extruded adhesive film of any one of claims 1 to 15 . 17. A double glazing comprising two glass layers and an adhesive film layer sandwiched between the glass layers, wherein the adhesive film layer is any one of claims 1 to 15 The co-extruded film described in the item.