CN111454668B

CN111454668B - Co-extrusion adhesive film, solar cell module and double-layer glass

Info

Publication number: CN111454668B
Application number: CN202010287647.2A
Authority: CN
Inventors: 魏梦娟; 唐国栋; 周光大
Original assignee: Hangzhou First Applied Material Co Ltd
Current assignee: Hangzhou First Applied Material Co Ltd
Priority date: 2020-04-13
Filing date: 2020-04-13
Publication date: 2022-04-15
Anticipated expiration: 2040-04-13
Also published as: CN111454668A

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-extrusion adhesive film, solar cell module and double-layer glass

Technical Field

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

Background

In a solar module, a photovoltaic co-extrusion film is used as the only 'barrier' of a silicon wafer and outer-layer glass, and in order to ensure that the solar module has higher photoelectric conversion efficiency, the co-extrusion film needs to have excellent barrier property, mechanical property, creep resistance and the like, and the above properties of the photovoltaic co-extrusion film are closely related to the crosslinking degree of the photovoltaic co-extrusion film. In addition, in order to avoid glue overflow in the lamination process, the fluidity of the glue film in the lamination process needs to be reduced, and the fluidity of the glue film is generally controlled by regulating the pre-crosslinking degree of the glue film.

Currently, adhesive film crosslinking is generally performed by the following method: chemical crosslinking, radiation crosslinking, ultraviolet crosslinking, and thermal crosslinking. The chemical crosslinking is generally to add a crosslinking agent and an auxiliary crosslinking agent in the adhesive film. In the laminating process, after the adhesive film is heated, the crosslinking agent (such as organic peroxide) is decomposed to generate free radicals, and the crosslinking reaction between the matrix resin and the auxiliary crosslinking agent is initiated, so that the enhancement of the mechanical property and the thermal creep resistance is realized. However, such a cross-linking system requires a long reaction time, which severely reduces the efficiency of the device fabrication and increases the cost of the device fabrication. And because the difference of the linear expansion coefficients of the materials of all layers in the assembly can generate a part of internal stress, the temperature of the assembly is reduced to room temperature after the assembly is packaged, and a part of internal stress is generated due to the difference of the heat conductivity coefficients of all the parts. The build-up of internal stresses in the two parts eventually leads to delamination, blistering, wrinkling, etc. between the components, but residual peroxide in the components can cause "snaking" problems and can also lead to corrosion of the solder strips, bus bars or cell plates in the components. The irradiation crosslinking and the ultraviolet crosslinking need special equipment, the production cost is increased, and the process flow is more complex.

The method for reducing the fluidity of the adhesive film mainly comprises the steps of adopting a low-melting-index resin raw material, irradiation pre-crosslinking treatment and the like. Wherein, the adoption of the low-melting resin can greatly improve the difficulty of the casting and extrusion of the adhesive film, greatly improve the production cost and limit the reduction of the flowability of the adhesive film. The most common processing method for white high-reflectivity adhesive films is to adopt ultraviolet irradiation treatment or electron beam irradiation treatment to ensure that the adhesive films have certain pre-crosslinking degree, but the methods have higher equipment and process cost, and the pre-crosslinking process can influence the reliability of the adhesive films.

Disclosure of Invention

The invention mainly aims to provide a co-extrusion adhesive film, a solar cell module and double-layer glass, and aims to solve the problems that the co-extrusion adhesive film prepared by the prior art is easy to delaminate, and the preparation period is influenced by long crosslinking time.

In order to achieve the above object, according to one aspect of the present invention, there is provided a co-extrusion adhesive film, including at least two adhesive film layers, wherein the raw materials for forming each adhesive film layer include, by weight, a first component and a second component, the first component includes 1 to 100 parts of a first matrix resin grafted with an electron-withdrawing group, the second component includes 0.01 to 25 parts of a water-producing agent and/or 0.01 to 2.5 parts of a catalyst, and each second component is not a water-producing agent at the same time or a catalyst at the same time, the first matrix resin and the water-producing agent may undergo a cross-linking reaction, and the catalyst is capable of catalyzing the cross-linking reaction.

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

Further, the silane coupling group is a free radical obtained by the reaction of the ethylene copolymer and a silane organic matter; preferably, the silane organic is selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-tert-butylhydroperoxide, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-glycidoxypropyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane.

Further, the water generating agent in the raw material for forming each gel film layer is selected from one or more of a single compound containing crystal water, a mixture of a metal oxide and an acid, a mixture of a metal hydroxide and an acid, and an organic matter containing at least two active groups, and each active group is independently selected from an amino group, a carboxyl group, a hydroxyl group, a mercapto group or an acetal group.

Further, the single compound containing crystal water is selected from one or more of calcium disulphate monohydrate, sodium carbonate monohydrate, calcium sulphate dihydrate, copper nitrate trihydrate, copper sulphate pentahydrate, magnesium sulphate hexahydrate, zinc sulphate heptahydrate, sodium carbonate heptahydrate, ferrous sulphate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulphate decahydrate, sodium carbonate decahydrate and aluminium potassium sulphate 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 one or more of zinc hydroxide, tin hydroxide, calcium hydroxide, magnesium hydroxide and aluminum hydroxide; the acid is selected from organic acids, preferably one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, pyroligneous acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, tridecanoic acid, tetracosanoic acid, pentacosanoic acid and hexacosanoic acid.

Further, the organic substance containing two or more active groups is one or more selected from the group consisting of 1, 3-propanediol, 1, 3-butanediol, ethylene glycol, ethylenediamine, triethanolamine, tetrahydroxypropylethylenediamine, maleic acid, fumaric acid, N-dimethylformamide, N-methylolacrylamide, N-hydroxyethylacrylamide, and p-hydroxyphenol.

Further, the catalyst in the raw material for forming each adhesive film layer is independently selected from one or more of organic amine, alcohol amine organic matter, piperazine organic matter, morpholine organic matter, bis (2-dimethylaminoethyl) ether, 1,8 diazabicyclo [5,4,0] undec-7-ene, pyridine organic matter, 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine, phenol organic matter, carboxylate, organic acid, polyhydric alcohol, tin-containing organic matter, bismuth-containing organic matter and lead-containing organic matter.

Further, the organic amine is selected from one or more of the group consisting of N, N-dimethylbenzylamine, N-dimethylcyclohexylamine, triethylenediamine, N ', N-tetramethylalkylenediamine, N', N-pentamethyldiethylenetriamine, triethylamine, N ', N-dimethylhexadecylamine, N', N-dimethylbutylamine, triethylenediamine; the alkanolamine organic matter is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N ', N-dimethylethanolamine and N, N' -bis (2-hydroxypropyl) aniline; the piperazine-based organic compound is one or more selected from the group consisting of 1, 4-dimethylpiperazine, N ', N-diethylpiperazine, N ', N-diethyl-2-methylpiperazine and N ', N-bis- (α -hydroxypropyl) -2-methylpiperazine; the morpholine organic matter is one or more selected from the group consisting of N-ethyl morpholine, N-methyl morpholine and N-2-hydroxypropyl dimethyl morpholine; the pyridine organic matter is one or more selected from the group consisting of pyridine, N', N-dimethylpyridine, alkylpyridine, halogenated pyridine, aminopyridine, methylpyridine, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine and dihydropyridine; the phenolic organic matter is selected from one or more of the group consisting of 2-methylphenol, 1, 3-benzenediol, 2, 4-dimethylphenol, 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 methylenebis-benzotriazolyl tetramethylbutylphenol; the carboxylate is selected from one or more of potassium acetate, zinc acetate, calcium acetate and magnesium acetate; the organic acid is selected from one or more of the group consisting of naphthalene sulfonic acid, toluene sulfonic acid, dodecylbenzene sulfonic acid and trimethyl-N-2-hydroxypropyl hexanoic acid; the polyhydric alcohol is one or more selected from the group consisting of ethylene glycol, glycerol, trimethylolethane and pentaerythritol; the tin-containing organic substance is one or more selected from the group consisting of dibutyltin dilaurate, stannous octoate, dioctyltin dithiolate, dibutyltin oxide, dibutyltin diacetate, dibutyltin bis (dodecylthio) and dibutyltin laurate maleate.

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

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

The utility model provides a solar module is still provided to another aspect of this application, including crowded glued membrane altogether, crowded glued membrane altogether is the crowded glued membrane altogether that this application provided altogether.

The application further provides double-layer glass, the double-layer glass comprises two glass layers and an adhesive film layer clamped between the glass layers, and the adhesive film layer is a co-extrusion adhesive film provided by the application.

By applying the technical scheme of the invention, the co-extruded adhesive film does not generate water during extrusion processing, the temperature is above 120 ℃ during the lamination process, the water generating agent in the raw materials of each adhesive film layer can generate water through physical reaction or chemical reaction, and the water can initiate the first matrix resin grafted with the electron-withdrawing group to generate crosslinking reaction to form a crosslinking network. Meanwhile, in the application process, after each glue film layer is melted, a little permeation can occur to the raw materials near the contact surface of the adjacent glue film layers, and under the action of the catalyst, the water generating agent in the raw materials of the adjacent glue film layers and the first matrix resin grafted with the electron-withdrawing group can be subjected to interlayer crosslinking or both of the interlayer crosslinking and the interlayer crosslinking. Under the two reasons, the purpose of rapid and efficient crosslinking can be achieved in the application process of the co-extrusion adhesive film without adding a free radical initiator and a bridging agent in the preparation process of the co-extrusion adhesive film, the adhesive property between adjacent adhesive film layers is greatly improved, and the effect of reducing the delamination risk of the co-extrusion adhesive film is achieved. In addition, the use amount of each component in the raw materials is limited within a specific range, so that the fluidity of the co-extruded adhesive film in the application process can be reduced, the crosslinking degree of the co-extruded adhesive film is controlled, and the comprehensive properties such as viscosity property, mechanical property, creep resistance and the like of the co-extruded adhesive film are improved. 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.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As described in the background art, the coextruded adhesive film prepared by the prior art has the problems of easy delamination and long crosslinking time which affects the preparation period. In order to solve the technical problem, the application provides a co-extrusion adhesive film, which 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, the second component is not water producing agent at the same time, nor is catalyst at the same time, the first matrix resin and the water producing agent can generate a cross-linking reaction, and the catalyst can catalyze the cross-linking reaction.

The co-extruded adhesive film does not generate water during extrusion processing, the temperature is above 120 ℃ during lamination, the water generating agent in the raw materials of each adhesive film layer can generate water through physical reaction or chemical reaction, and the water can initiate the first matrix resin grafted with the electron-withdrawing group to generate crosslinking reaction to form a crosslinking network. And simultaneously, after the glue film layers are melted in the application process, under the action of a catalyst, the water generating agent in the raw materials of the adjacent glue film layers and the first matrix resin grafted with the electron-withdrawing group can be subjected to interlayer crosslinking or intralayer crosslinking and interlayer crosslinking. Under the two reasons, the purpose of rapid and efficient crosslinking can be achieved in the application process of the co-extrusion adhesive film without adding a free radical initiator and a bridging agent in the preparation process of the co-extrusion adhesive film, the adhesive property between adjacent adhesive film layers is greatly improved, and the effect of reducing the delamination risk of the co-extrusion adhesive film is achieved. In addition, the use amount of each component in the raw materials is limited within a specific range, so that the fluidity of the co-extruded adhesive film in the application process can be reduced, the crosslinking degree of the co-extruded adhesive film is controlled, and the comprehensive properties such as viscosity property, mechanical property, creep resistance and the like of the co-extruded adhesive film are improved.

The pre-crosslinking degree of the co-extruded adhesive film prepared from the raw materials is 5-70%, and the peel strength of the co-extruded adhesive film and glass is greater than 65N/cm. Therefore, 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.

The electron-withdrawing group grafted on the first matrix resin can improve the crosslinking degree inside each adhesive film layer and between adjacent layers, and further is favorable for improving the mechanical property, the barrier property and the like of the co-extruded adhesive film. In a preferred embodiment, the electron-withdrawing group in each first base resin is independently selected from one or more of an acid anhydride group, an isocyanate group, a silane coupling group, an acid chloride group, an amino group, a carboxyl group, a hydroxyl group, a mercapto group, a sulfonic acid group, an epoxy group and a cyano group. Compared with other electron-withdrawing groups, the electron-withdrawing groups have better crosslinking activity, so that the crosslinking degree, the mechanical property, the barrier property and the like of the co-extrusion adhesive film are further improved.

In a preferred embodiment, the silane coupling group is a radical derived from the reaction of an ethylene copolymer with a silane organic. The silane coupling group is selected as the electron-withdrawing group, so that the use amount of the cross-linking agent and the auxiliary cross-linking agent in the formed co-extruded adhesive film can be reduced, even the cross-linking agent and the auxiliary cross-linking agent are not needed, the resin matrix can be cross-linked, the formula contains a small amount of or does not contain the polar small-molecule auxiliary agent, the residual of the auxiliary agent after the co-extruded adhesive film is laminated is greatly reduced, the adverse effect caused by precipitation and migration of the polar small-molecule auxiliary agent in the processing and storage processes of the adhesive film is avoided, the problems of bubbles, snail marks and the like in the manufacturing process of the assembly are reduced, and the production cost of the co-extruded adhesive film is further reduced; meanwhile, the laminating time can be shortened, and the production efficiency can be improved. To further enhance the reactivity of the electron-withdrawing group, more preferably, the silane organic includes, but is not limited to, one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-tert-butylperoxy silane, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, γ -glycidoxypropyltrimethoxysilane, or γ -methacryloxypropyltrimethoxysilane.

In order to further improve the crosslinking degree of the co-extruded adhesive film during the application process and further improve the comprehensive performance of the co-extruded adhesive film, in a preferred embodiment, in the first base resin grafted with the electron-withdrawing group, the grafting amount of the electron-withdrawing group is 0.1 to 10wt%, preferably 0.5 to 3%, more preferably 0.6 to 2.8%, and further preferably 1 to 2.5%.

The water generating agent is heated to generate physical or chemical reaction to generate water, and then the water initiates the first matrix resin grafted with the electron-withdrawing group to generate crosslinking reaction to form a crosslinking network, so that the comprehensive performance of the co-extrusion adhesive film is improved. In a preferred embodiment, the water generating agent in the raw material forming each glue film layer is selected from one or more of a single compound containing water of crystallization, a mixture of metal oxide and acid, and an organic substance containing at least two reactive groups, and each of the reactive groups is independently selected from amino, carboxyl, hydroxyl, mercapto or acetal group.

Because the temperature of the co-extruded film in the application process is higher, a single compound containing the crystal water can generate water through physical reactions such as heating and the like in the application process, and the temperature of the co-extruded film in the extrusion processing is lower, so that the water is not generated. In a preferred embodiment, the water producing agent is selected from one or more of calcium disulphate monohydrate, sodium carbonate monohydrate, calcium sulphate dihydrate, copper nitrate trihydrate, copper sulphate pentahydrate, magnesium sulphate hexahydrate, zinc sulphate heptahydrate, sodium carbonate heptahydrate, ferrous sulphate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulphate decahydrate, sodium carbonate decahydrate and aluminium potassium sulphate dodecahydrate.

In another preferred embodiment, the water generating agent is a mixture of a metal oxide and an acid, or a mixture of a metal hydroxide and an acid, the acid is selected from one or more of inorganic acid and/or organic acid, metal oxide zinc oxide, 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. Acids can release hydrogen ions and thus, when used in conjunction with metal oxides or metal hydroxides, can produce water through a chemical reaction. In order to further improve the light transmittance of the co-extruded film, preferably, the metal oxide or metal hydroxide is nano-scale 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, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlitic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, pyroligneous acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, hentriacontanoic acid, tridecanoic acid, tetracosanoic acid, pentacosanoic acid, or hexacosanoic acid. In order to further improve the compatibility of the acid with the matrix resin, the acid is preferably selected from fatty acids having more than 10 carbon atoms. The hard fatty acid is more convenient to obtain and has lower cost.

In still another preferred embodiment, the organic compound having two or more reactive groups includes, but is not limited to, one or more of 1, 3-propanediol, 1, 3-butanediol, ethylene glycol, ethylenediamine, triethanolamine, tetrahydroxypropylethylenediamine, maleic acid, fumaric acid, N-dimethylformamide, N-methylolacrylamide, N-hydroxyethylacrylamide, and p-hydroxyphenol. Compared with other water-producing agents, the water-producing agent has better compatibility with other raw materials for forming the co-extrusion adhesive film, so that the water-producing agent is more uniform in dispersion, better in crosslinking effect during application and higher in performance stability of the co-extrusion adhesive film.

In a preferred embodiment, the catalyst in the raw material for forming each adhesive film layer is independently selected from one or more of organic amine, alcohol amine organic compound, piperazine organic compound, morpholine organic compound, bis (2-dimethylaminoethyl) ether, 1,8 diazabicyclo [5,4,0] undec-7-ene, pyridine organic compound, 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine, phenol organic compound, carboxylate, organic acid, polyhydric alcohol, tin-containing organic compound, bismuth-containing organic compound and lead-containing organic compound. Compared with other catalysts, the catalyst is favorable for further improving the crosslinking degree of the high-yield agent and the first matrix resin grafted with the electron-withdrawing group, and the comprehensive performance of the adhesive film is improved.

More preferably, the organic amine includes, but is not limited to, one or more of the group consisting of N, N-dimethylbenzylamine, N-dimethylcyclohexylamine, triethylenediamine, N ', N-tetramethylalkylenediamine, N ' -pentamethyldiethylenetriamine, triethylamine, N ', N-dimethylbenzylamine, N ', N-dimethylhexadecylamine, N ', N-dimethylbutylamine, triethylenediamine; the alkanolamine organic substance includes, but is not limited to, one or more of the group consisting of ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N ', N-dimethylethanolamine and N, N' -bis (2 hydroxypropyl) aniline; piperazine-based organic compounds include, but are not limited to, one or more of the group consisting of 1, 4-dimethylpiperazine, N ', N-diethylpiperazine, N ', N-diethyl-2-methylpiperazine and N ', N-bis- (α -hydroxypropyl) -2-methylpiperazine; morpholine-based organics include, but are not limited to, one or more of the group consisting of N-ethyl morpholine, N-methyl morpholine, and N-2-hydroxypropyl dimethyl morpholine; pyridine-based organic compounds include, but are not limited to, one or more of the group consisting of pyridine, N', N-lutidine, alkylpyridine, halopyridine, aminopyridine, picoline, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine, dihydropyridine; the phenolic organic matter is selected from one or more of the group consisting of 2-methyl phenol, 1, 3-benzenediol, 2, 4-dimethyl phenol, 2, 6-dimethyl phenol, 2,4, 6-tri (dimethylaminomethyl) phenol, 2, 6-di-tert-butyl-4-methyl phenol, 2, 6-di-tert-butyl-4-ethyl phenol, 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1, 1-dimethylethyl) -4-methyl phenol and methylene bis-benzotriazolyl tetramethyl butyl phenol; the carboxylate is selected from one or more of potassium acetate, zinc acetate, calcium acetate and magnesium acetate; the organic acid is selected from one or more of the group consisting of naphthalene sulfonic acid, toluene sulfonic acid, dodecylbenzene sulfonic acid and trimethyl-N-2-hydroxypropyl hexanoic acid; the polyhydric alcohol is one or more selected from the group consisting of ethylene glycol, glycerol, trimethylolethane and pentaerythritol; the tin-containing organic substance is one or more selected from the group consisting of dibutyltin dilaurate, stannous octoate, dioctyltin dithiolate, dibutyltin oxide, dibutyltin diacetate, dibutyltin bis (dodecylthio) and dibutyltin laurate maleate.

In a preferred embodiment, the raw materials for forming each adhesive film layer independently comprise 0-99 parts by weight of the second matrix resin, 0-5 parts by weight of the peroxide crosslinking agent, 0-5 parts by weight of the co-crosslinking agent, 0-1 part by weight of the light stabilizer, 0-2 parts by weight of the ultraviolet absorber, 0-3 parts by weight of the tackifier and 0-40 parts by weight of the pigment. More preferably, the raw materials for forming each glue film layer independently comprise, by weight, 1 to 100 parts of the first base resin grafted with an electron-withdrawing group, 5 to 90 parts of the second base resin, 0.1 to 2 parts of the crosslinking agent, 0.1 to 3 parts of the auxiliary crosslinking agent, 0.1 to 1 part of the light stabilizer, 0.1 to 1 part of the ultraviolet absorber, 0.1 to 1 part of the tackifier, 0 to 20 parts of the pigment, and 0.1 to 10 parts of the water generating agent and/or 0.05 to 1 part of the catalyst.

The addition of the second matrix resin is favorable for improving the mechanical property and the barrier property of the co-extruded adhesive film, the addition of the peroxide crosslinking agent and the auxiliary crosslinking agent is favorable for further improving the crosslinking property of the co-extruded adhesive film, the addition of the light stabilizer is favorable for improving the light stability of the co-extruded adhesive film, the addition of the ultraviolet light absorbent is favorable for improving the aging resistance of the co-extruded adhesive film, the addition of the tackifier is favorable for improving the viscosity of the co-extruded adhesive film, further, the delamination risk in the subsequent application process is favorably further reduced, and the addition of the pigment can meet the requirements of a user on color.

In a preferred embodiment, the first matrix resin and the second matrix resin in the raw material forming each adhesive film layer are each independently selected from an ethylene copolymer or an ethylene- α -olefin copolymer, wherein the ethylene copolymer is a copolymer of ethylene and one or more polymerized monomers including, but not limited to, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, butadiene, 1, 4-pentadiene, isoprene, ethylidene norbornene, dicyclopentadiene, a binary or multicomponent copolymer of 1, 4-hexadiene, polyvinyl butyral, a block copolymer of butadiene/isoprene and styrene, natural rubber or trans-polyisoprene rubber; the ethylene-alpha-olefin copolymer is obtained by polymerizing ethylene and one or more alpha-olefins with 3-20 carbon atoms, and more preferably, the alpha-olefin comprises but is not limited to propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-dodecene. Compared with other matrix resins, the resin is selected as the first matrix resin or the second matrix resin, so that the comprehensive properties of the co-extrusion adhesive film, such as mechanical property, barrier property and the like, can be further improved.

The peroxide crosslinking agent may be selected from those conventionally used in the art. In a preferred embodiment, the peroxide-based crosslinking agent in the raw material for forming each of the film layers is independently selected from isopropyl t-butylperoxycarbonate, 2, 5-dimethyl-2, 5- (di-t-butylperoxy) hexane, 2-ethylhexyl t-butylperoxycarbonate, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-amylperoxy) cyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane, t-amyl peroxy-2-ethylhexylcarbonate, 2, 5-dimethyl-2, one or more of 5-bis (benzoylperoxy) -hexane, t-amyl peroxycarbonate, and t-butyl peroxy3, 3, 5-trimethylhexanoate.

The tackifier may be selected from those conventionally used in the art. In a preferred embodiment, the adhesion promoter in the raw materials forming each adhesive film layer is independently selected from one or more of gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethylsilane and 3-aminopropyltrimethylsilane. Compared with other tackifiers, the selected tackifiers are favorable for further improving the compatibility of each component in the adhesive film layer, so that the adhesive property of the co-extruded adhesive film is further improved.

The auxiliary crosslinking agent may be selected from those commonly used in the art. In order to further increase the degree of crosslinking of the coextruded film, the crosslinking coagents in the raw materials forming each film layer are preferably independently selected from triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4, 6-tris (2-propenyloxy) -1,3, 5-triazine, tricyclodecane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and polyethylene glycol dimethacrylate.

The pigment in the raw materials can be selected from the types commonly used in the field, such as one or more of hollow glass beads, calcium carbonate, barium sulfate, talcum powder, titanium dioxide, zinc oxide, carbon black, graphene oxide, copper-chromium black, magnesium hydroxide, aluminum oxide, magnesium oxide, boron nitride, silicon carbide, ammonium phosphate, ammonium polyphosphate, pentaerythritol, dipentaerythritol, pentaerythritol ester and melamine polyphosphate borate.

In a preferred embodiment, the light stabilizer in the raw material for forming each film layer is independently selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, 4- (meth) acryloyloxy-2, 2,6, 6-tetramethylpiperidine and graft copolymer obtained by polymerizing alpha-olefin monomer, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, 3, 5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol and tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite. Compared with other light stabilizers, the light stabilizers are favorable for further improving the light stability of the co-extruded film, so that the service life of the co-extruded film is prolonged.

In a preferred embodiment, the ultraviolet light absorbers in the raw materials forming each adhesive film layer are independently selected from one or more of 2-hydroxy-4-n-octoxybenzophenone, 2-tetramethylene bis (3, 1-benzoxazin-4-one), 2- (2 ' -hydroxy-5-methylphenyl) benzotriazole and 2,2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone. Compared with other light stabilizers, the light stabilizers are favorable for further improving the aging resistance and the like of the co-extruded film.

This application on the other hand still provides a solar module, including crowded glued membrane altogether, and this crowded glued membrane altogether is the crowded glued membrane altogether that this application provided.

The co-extruded adhesive film has the advantages of good adhesive property, barrier property, mechanical property, creep resistance, high stability and reliability, and difficult delamination. Therefore, the solar cell module containing the co-extrusion adhesive film has the advantages of higher photoelectric conversion efficiency, low cost, simple process and convenience for industrial popularization.

The application further provides double-layer glass, which comprises two glass layers and an adhesive film layer sandwiched between the glass layers, wherein the adhesive film layer is the co-extrusion adhesive film provided by the application.

The co-extruded adhesive film has the advantages of good adhesive property, barrier property, mechanical property, creep resistance, high stability and reliability, and difficult delamination. Therefore, the double-layer glass containing the co-extrusion adhesive film has better lamination performance, good barrier property and mechanical property, low cost, simple process and convenient industrial popularization.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

Example 1

Raw materials of the first adhesive film layer: by weight, 30 parts of matrix resin ethylene-vinyl acetate copolymer (VA content of 28 wt%, DuPont USA) and 70 parts of vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer (VA content of 28 wt%, grafting rate of 2 wt%, DuPont USA) are taken, and 1.5 parts of catalyst N, N-dimethylbenzylamine, 0.8 part of cross-linking agent 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 0.8 part of auxiliary cross-linking agent trimethylolpropane trimethacrylate are added.

The raw materials of the second adhesive film layer: by weight, 10 parts of matrix resin ethylene-hexene copolymer (Dow.) and 80 parts of vinyl trimethoxy silane grafted ethylene-hexene copolymer (grafting rate 2 wt%, Dow.) and 10 parts of water producing agent calcium dithionate master batch and 10 parts of water producing agent 1, 3-propylene glycol are taken. Wherein, the calcium sulfate monohydrate master batch is obtained by granulating calcium dithionite and ethylene-hexene copolymer through a double-screw extruder, and the dosage of the calcium sulfate monohydrate is 20 parts relative to 100 parts of the ethylene-octene copolymer.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. And respectively melting and plasticizing the extrusion material of the first adhesive film layer and the extrusion material of the second adhesive film layer, injecting the melted and plasticized extrusion materials into the same die head, combining the two layers to form a melt flow in the T die head, preparing a double-layer composite photovoltaic co-extrusion adhesive film through the processes of melting extrusion, casting film forming, cooling, slitting, rolling and the like, and marking as E1, wherein the thickness of the second adhesive film layer is 0.2mm and the thickness of the first adhesive film layer is 0.3mm according to the calculation of a distributor.

Example 2

Raw materials of the first adhesive film layer: by weight, 100 parts of isocyanate group grafted ethylene-octene copolymer (grafting ratio 3 wt%, Dow USA), 1 part of catalyst ethylene glycol, 0.01 part of catalyst stannous octoate, 2 parts of cross-linking agent 1, 1-bis (t-amyl peroxy) cyclohexane, 0.02 part of auxiliary cross-linking agent trimethylolpropane triacrylate, 1.0 part of auxiliary cross-linking agent ethoxylated glycerol triacrylate, 0.8 part of tackifier vinyl tri-peroxy-t-butyl silane, 0.8 part of light stabilizer bis-2, 2,6, 6-tetramethyl piperidinol sebacate and 20 parts of titanium dioxide.

The raw materials of the second adhesive film layer: based on parts by weight, 100 parts of an isocyanate group grafted ethylene-octene copolymer (grafting ratio 3 wt%, Dow. USA), 5 parts of a water producing agent (master batch of calcium oxide and lauric acid), and 20 parts of 1, 4-butanediol. The master batch of calcium oxide and lauric acid is obtained by granulating a copolymer of calcium oxide, lauric acid and ethylene-octene (Dow, USA) through a double-screw extruder, wherein the calcium oxide accounts for 3 parts and the lauric acid accounts for 10 parts relative to 100 parts of the copolymer of ethylene-octene.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extrusion material of the first adhesive film layer and the extrusion material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer, the second adhesive film layer and the first adhesive film layer three-layer composite photovoltaic co-extrusion adhesive film are prepared through the processes of melting extrusion, tape casting film forming, cooling, slitting, rolling and the like, the mark is E2, and the thickness of the second adhesive film layer is 0.1mm, the thickness of the first adhesive film layer is 0.2mm and the total thickness of the adhesive film is 0.5mm according to calculation of a distributor.

Example 3

Raw materials of the first adhesive film layer: 50 parts by weight of a matrix resin ethylene-propylene copolymer (Dow. USA), 50 parts by weight of an ethylene-propylene copolymer (Dow. USA) containing 1.0% of anhydride, 2.5 parts by weight of catalyst triethylenediamine, 0.5 part by weight of crosslinking agent tert-butyl peroxyisopropyl carbonate, 0.9 part by weight of co-crosslinking agent triallyl isocyanurate, 0.5 part by weight of tackifier vinyltriethoxysilane, and 0.02 part by weight of light stabilizer bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.

The raw materials of the second adhesive film layer: 20 parts by weight of an ethylene-propylene copolymer (Dow. USA) containing 1.0% of anhydride, 80 parts of an ethylene-pentene copolymer (Dow. USA) containing 1.2% of sulfydryl, 0.5 part of a catalyst N, N-dimethylcyclohexylamine, 2 parts of a first crosslinking agent 1, 1-bis (t-amylperoxy) cyclohexane, 0.02 part of a co-crosslinking agent trimethylolpropane triacrylate, 0.8 part of a first crosslinking agent vinyl tri-peroxy-t-butylsilane, 0.8 part of a light stabilizer bis-2, 2,6, 6-tetramethylpiperidinol sebacate, and 2 parts of a tackifier gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extruded materials of the first adhesive film layer and the extruded materials of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer, the second adhesive film layer, the first adhesive film layer and the second adhesive film layer are prepared through the processes of melting extrusion, tape casting film forming, cooling, slitting, rolling and the like, the four-layer composite photovoltaic co-extruded adhesive film is marked as E3, and the thickness of the second adhesive film layer, the thickness of the first adhesive film layer and the total thickness of the adhesive film are 0.1mm, 0.1mm and 0.4mm respectively through a distributor.

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% of silane coupling group, 50 parts of ethylene-pentene copolymer containing 1.5% of hydroxyl group (Dow. USA), 1 part of catalyst trimethyl-N-2-hydroxypropyl hexanoic acid, 2 parts of cross-linking agent tert-butyl peroxycarbonic acid-2-ethylhexyl ester, 1 part of auxiliary cross-linking agent diethylene glycol dimethacrylate, 0.8 part of light stabilizer tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite and 40 parts of pigment carbon black.

The raw materials of the second adhesive film layer: the preparation method comprises the following steps of taking 20 parts by weight of ethylene-propylene copolymer (Dow USA), 80 parts by weight of ethylene-pentene copolymer (Dow USA) containing 1.5% of hydroxyl, 0.5 part by weight of water-producing agent ethylene glycol, 0.5 part by weight of catalyst N', N-dimethyl hexadecylamine, 2 parts by weight of auxiliary cross-linking agent ethyl tert-butyl peroxyisopropyl carbonate, 1 part by weight of auxiliary cross-linking agent diethylene glycol dimethacrylate and 0.8 part by weight of light stabilizer tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extruded materials of the first adhesive film layer and the extruded materials of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer, the second adhesive film layer and the first adhesive film layer five-layer composite photovoltaic co-extruded adhesive film are prepared through the processes of melting extrusion, tape casting film forming, cooling, slitting, rolling and the like, the thickness of the second adhesive film layer of the co-extruded adhesive film is marked as E4, and the thickness of the first adhesive film layer is 0.1mm and the total thickness of the adhesive film is 0.7mm according to calculation of a distributor.

Example 5

Raw materials of the first adhesive film layer: 10 parts of matrix resin ethylene-methyl methacrylate copolymer (Dow USA), 35 parts of ethylene-pentene copolymer (Dow USA) containing 2.5% of silane coupling group, 35 parts of ethylene-octene copolymer (Dow USA) containing 6.5% of sulfonic group, 20 parts of ethylene-butene copolymer (Dow USA) containing 2.5% of isocyanate group, 0.3 part of catalyst N ', N ', N ', N-pentamethyldiethylenetriamine, 0.5 part of co-crosslinking agent 2,4, 6-tri (2-propenyl oxy) -1,3, 5-triazine, 0.9 part of light stabilizer bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 3 parts of pigment titanium dioxide and 2 parts of pigment hollow glass bead

The raw materials of the second adhesive film layer: 10 parts by weight of an ethylene-methyl methacrylate copolymer (DuPont, USA), 35 parts by weight of an ethylene-pentene copolymer (Dow, USA) containing 2.5% of a silane coupling group, 35 parts by weight of an ethylene-octene copolymer (Dow, USA) containing 6.5% of a sulfonic acid group, and 20 parts by weight of master batches containing zinc oxide and stearic acid. The master batch containing zinc oxide and stearic acid is obtained by granulating zinc oxide, stearic acid and ethylene-octene copolymer through a double-screw extruder, wherein relative to 100 parts of ethylene-octene copolymer, the calcium oxide is 2 parts, and the lauric acid is 7 parts. 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-tetramethyl-4-piperidyl) sebacate, 0.8 part of 2- (2' -hydroxy-5-methylphenyl) benzotriazole were added.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extrusion material of the first adhesive film layer and the extrusion material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer and the second adhesive film layer are prepared through the processes of melting extrusion, casting film forming, cooling, slitting, rolling and the like, the thickness of the second adhesive film layer of the co-extruded adhesive film is marked as E5, and the thickness of the first adhesive film layer is 0.25mm, and the total thickness of the adhesive film is 0.45mm according to the calculation of a distributor.

Example 6

Raw materials of the first adhesive film layer: 100 parts of an ethylene-pentene copolymer (Dow. USA) containing 2.0% of a silane coupling group and 2.5% of an acid chloride group, 0.4 part of a catalyst triethylenediamine, 1.0 part of a crosslinking agent 1, 1-bis (t-amylperoxy) -3,3, 5-trimethylcyclohexane, 1.0 part of a co-crosslinking agent diethylene glycol dimethacrylate, 0.05 part of a light stabilizer bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, and 0.8 part of a second ultraviolet light absorber 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone.

The raw materials of the second adhesive film layer: 55 parts by weight of an ethylene-pentene copolymer (Dow USA) containing 3.5% of a silane coupling group, 45 parts by weight of an ethylene-octene copolymer (Dow USA) containing 3.5% of an isocyanate group, 1.0 part by weight of 1, 4-butanediol as a water-producing agent, 0.5 part by weight of ethylenediamine as a water-producing agent containing 2.5% of an amino group, 0.5 part by weight of triethanolamine as a water-producing agent, 1.0 part by weight of 1, 1-bis (tert-amylperoxy) -3,3, 5-trimethylcyclohexane as a crosslinking agent, 1.0 part by weight of diethylene glycol dimethacrylate as a co-crosslinking agent, 0.5 part by weight of hexadecyl 3, 5-di-tert-butyl-4-hydroxy-benzoate as a light stabilizer, and 0.8 part by weight of 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone as a second ultraviolet light absorber.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extrusion material of the first adhesive film layer and the extrusion material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer and the second adhesive film layer are prepared through the processes of melting extrusion, casting film forming, cooling, slitting, rolling and the like, the thickness of the second adhesive film layer of the co-extruded adhesive film is marked as E6, and the thickness of the first adhesive film layer is 0.25mm, and the total thickness of the adhesive film is 0.45mm according to the calculation of a distributor.

Example 7

The difference from the embodiment 1 is that,

raw materials of the first adhesive film layer: taking 100 parts by weight of base resin grafted with an electron-withdrawing group (vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer, the VA content is 28 wt%, the grafting rate is 2 wt%, Dupont USA) and 0.01 part of catalyst (N, N-dimethyl benzylamine);

the raw materials of the second adhesive film layer: based on the parts by weight, 1 part of a base resin grafted with an electron-withdrawing group (vinyltrimethoxysilane grafted ethylene-hexene copolymer, grafting rate 2 wt%, Dow. USA) and 25 parts of a water-producing agent (calcium dithionate monohydrate and 1, 3-propanediol in a weight ratio of 1:1) are taken.

Example 8

The difference from the embodiment 1 is that,

raw materials of the first adhesive film layer: taking 1 part by weight of base resin grafted with an electron-withdrawing group (vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer, the VA content is 28 wt%, the grafting rate is 2 wt%, Dupont USA) and 2.5 parts by weight of catalyst (N, N-dimethyl benzylamine);

the raw materials of the second adhesive film layer: based on the parts by weight, 100 parts of a base resin grafted with an electron-withdrawing group (vinyltrimethoxysilane grafted ethylene-hexene copolymer, grafting rate 2 wt%, Dow. USA) and 0.01 part of a water-producing agent (calcium dithionate monohydrate and 1, 3-propanediol in a weight ratio of 1:1) are taken.

Example 9

The difference from the embodiment 1 is that,

raw materials of the first adhesive film layer: based on parts by weight, 100 parts of base resin grafted with electron-withdrawing groups (vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer, VA content of 28 wt%, grafting rate of 2 wt%, DuPont, USA) are taken, 1.5 parts of catalyst N, N-methylbenzylamine, 0.8 part of cross-linking agent 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.8 part of auxiliary cross-linking agent trimethylolpropane trimethacrylate are added.

The raw materials of the second adhesive film layer: based on the parts by weight, 100 parts of base resin grafted with electron-withdrawing groups (vinyl trimethoxy silane grafted ethylene-hexene copolymer, grafting rate 2 wt%, Dow USA), 10 parts of master batch of water-producing agent calcium dithionate monohydrate, and 10 parts of water-producing agent 1, 3-propylene glycol are taken. The master batch of calcium sulfate monohydrate is obtained by granulating calcium dithionate monohydrate and ethylene-hexene copolymer through a double-screw extruder, and the using amount of the calcium oxalate monohydrate is 20 parts relative to 100 parts of the ethylene-octene copolymer.

Example 10

The difference from the embodiment 1 is that,

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

Example 11

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is an acyl chloride-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 2 wt%, DuPont, USA).

Example 12

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is an amino-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 2 wt%, U.S. DuPont).

Example 13

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a carboxyl grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 2 wt%, U.S. DuPont).

Example 14

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is ethylene-vinyl acetate copolymer grafted by sulfonic acid group (VA content is 28 wt%, grafting rate is 2 wt%, U.S. DuPont).

Example 15

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is epoxy group grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 2 wt%, U.S. DuPont).

Example 16

The difference from the embodiment 1 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a cyano-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 2 wt%, U.S. DuPont).

Example 17

The difference from the embodiment 16 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a cyano-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 0.8 wt%, DuPont, USA).

Example 18

The difference from the embodiment 16 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a cyano-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 0.1 wt%, DuPont, USA).

Example 19

The difference from the embodiment 16 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a cyano-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 10wt%, U.S. DuPont).

Example 20

The difference from the embodiment 16 is that,

the base resin grafted with electron-withdrawing groups in the raw materials of the first adhesive film layer and the second adhesive film layer is a cyano-grafted ethylene-vinyl acetate copolymer (VA content is 28 wt%, grafting rate is 0.05 wt%, 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 from 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 a tackifier (gamma-aminopropyltriethoxysilane) was added to the raw material of the first adhesive film layer.

Example 29

The difference from example 28 is that the adhesion promoter is gamma-methacryloxypropyltrimethoxysilane.

Example 30

The difference from example 28 is that the adhesion promoter is gamma- (2, 3-glycidoxy) propyltrimethoxysilane.

Example 31

The difference from the embodiment 1 is that,

a first adhesive film layer: by weight, 30 parts of matrix resin ethylene-vinyl acetate copolymer (with the VA content of 28 wt%, DuPont USA) and 70 parts of vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer (with the VA content of 28 wt%, the grafting rate of 2 wt%, DuPont USA) are taken, 1.5 parts of catalyst N, N-methylbenzylamine, 10 parts of water producing agent calcium disulfide monohydrate, 0.8 part of crosslinking agent 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.8 part of auxiliary crosslinking agent trimethylolpropane trimethacrylate are added.

A second adhesive film layer: by weight, 10 parts of matrix resin ethylene-hexene copolymer (Dow. USA), 80 parts of vinyl trimethoxy silane grafted ethylene-hexene copolymer (grafting rate is 2 wt%, Dow. USA), 10 parts of water producing agent calcium dithionate monohydrate and 10 parts of water producing agent 1, 3-propylene glycol are taken. The master batch of calcium sulfate monohydrate is obtained by granulating calcium dithionate monohydrate and ethylene-hexene copolymer through a double-screw extruder, and the using amount of the calcium oxalate monohydrate is 20 parts relative to 100 parts of the ethylene-octene copolymer.

Comparative example 1

Raw materials of the first adhesive film layer: by weight, 30 parts of matrix resin ethylene-vinyl acetate copolymer (VA content of 28 wt%, DuPont USA) and 70 parts of vinyl trimethoxy silane grafted ethylene-vinyl acetate copolymer (VA content of 28 wt%, grafting rate of 2 wt%, DuPont USA) are taken, 0.8 part of cross-linking agent 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.8 part of auxiliary cross-linking agent trimethylolpropane trimethacrylate are added.

The raw materials of the second adhesive film layer: in parts by weight, 10 parts of a base resin ethylene-hexene copolymer (dow usa) and 80 parts of a vinyltrimethoxysilane grafted ethylene-hexene copolymer (graft ratio 2 wt%, dow usa) were taken.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. And the extruded materials of the first adhesive film layer and the extruded materials of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, a double-layer composite photovoltaic co-extrusion adhesive film is prepared through the processes of melt extrusion, tape casting film forming, cooling, slitting, rolling and the like, the thickness is marked as R1, and the thickness of the second adhesive film layer is 0.2mm and the thickness of the first adhesive film layer is 0.3mm according to calculation of a distributor.

Comparative example 2

A first adhesive film layer: based on parts by weight, 100 parts of matrix resin ethylene-pentene copolymer (Dow USA), 1.0 part of crosslinking agent 1, 1-bis (tert-amyl peroxy) -3,3, 5-trimethyl cyclohexane, 1.0 part of auxiliary crosslinking agent diethylene glycol dimethacrylate, 0.05 part of light stabilizer bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate and 0.8 part of ultraviolet light absorber 2,2 '-dihydroxy-4, 4' -dimethoxy benzophenone are taken.

A second adhesive film layer: 100 parts by weight of a matrix resin, namely an 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 and 0.8 part of 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone.

And respectively mixing the raw materials of the first adhesive film layer and the second adhesive film layer uniformly, and adding the mixture into different extruders. The extrusion material of the first adhesive film layer and the extrusion material of the second adhesive film layer are respectively melted and plasticized and then injected into the same die head, a melt flow is formed in the T die head in a combined mode, the first adhesive film layer and the second adhesive film layer are prepared through the processes of melting extrusion, casting film forming, cooling, slitting, rolling and the like, the R2 is marked, and the thickness of the second adhesive film layer of the co-extruded adhesive film, the thickness of the first adhesive film layer and the total thickness of the adhesive film are calculated through a distributor and can be 0.2mm, 0.25mm and 0.45 mm.

Comparative example 3

The difference from example 1 is that the amount of the water-generating agent was 30 parts and the amount of the catalyst was 3 parts.

The examples and comparative examples were tested for adhesion and degree of crosslinking and for comparison of the lamination characteristics of the assembly, reliability.

Test item and test method

1. Adhesive force

And (3) sequentially stacking the glass/adhesive film (two layers)/flexible back plate with the thickness of 300mm multiplied by 150mm, putting the stack into a vacuum laminating machine, and pressing the stack according to a lamination process of 150 ℃ for 18 minutes to manufacture the pressing piece.

The flexible backsheet/adhesive film was cut into 10mm ± 0.5mm test pieces every 5mm in the width direction for testing the adhesive force between the adhesive film and the glass. According to the test method of GB/T2790-1995, the peeling force between the adhesive film and the glass is tested on a tensile tester at a tensile speed of 100mm/min +/-10 mm/min, and the arithmetic mean of the three tests is taken to be accurate to 0.1N/cm.

2. Degree of crosslinking

The method of heating and extracting dimethylbenzene is adopted for testing. The ratio of the mass not dissolved in xylene to the initial mass is referred to as the degree of crosslinking. The arithmetic mean of the three samples is taken in%.

3. Evaluation of laminate appearance of Components

And (3) laminating according to the laminating sequence of glass/adhesive film/cell piece/adhesive film/glass, and laminating according to the laminating process of the adhesion test to manufacture a standard double-glass solar cell module, wherein the specification of the module is the plate type of 60 (6 multiplied by 10) cell pieces. According to different adhesive films, 100 assemblies are manufactured for appearance evaluation. The evaluation criteria take the occurrence of bubbles, impurities and delamination between an adhesive film and a battery piece or glass as judgment objects, and are as follows:

o: no Δ: slight x: severe severity of disease

4. And (3) testing the snail veins of the components:

and pressing the adhesive film, the battery piece, the back plate (WVTR is less than 2.0), the coated glass, the junction box and other material layers to prepare 4 small battery assembly samples.

After the battery is subfissure in the manufacturing process of the component sample, the battery is placed at 85 ℃ and 85% RH, and the power is supplied for 8A 168 h; after being taken out, the anode and the cathode of the sample junction box are short-circuited and are illuminated by 10kWh/m²This was used as one cycle, and 3 cycles were continuously performed. Before and after each cycle, the appearance of the sample was visually inspected to see whether snail marks appear 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 better adhesion with glass after lamination, and maintains good reliability, and the performance in terms of appearance and snail marks of the assembly is obviously better than that of the adhesive film of the comparative example and the assembly prepared therefrom.

Comparing examples 1, 7 to 8 and comparative example 3, it can be seen that limiting the amount of the water-generating agent to the preferred range of the present application is advantageous for improving the performance of the co-extruded packaging film.

Comparing examples 1, 9 to 20, it can be seen that the use of the preferred electron-withdrawing group grafted matrix resin of the present application is advantageous in improving the performance of the co-extruded encapsulation film.

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

Comparing examples 1, 28 to 30, it can be seen that the addition of tackifier, and the selection of tackifier preferred in the present application, is beneficial to improving the performance of the co-extruded packaging film.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A co-extrusion adhesive film is characterized by comprising at least two adhesive film layers, wherein 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 a water-producing agent and/or 0.01-2.5 parts of a catalyst, each second component is not the water-producing agent at the same time, nor the catalyst at the same time, the first matrix resin and the water-producing agent can generate a cross-linking reaction, and the catalyst can catalyze the cross-linking reaction;

the water generating agent in the raw material for forming each gel film layer is selected from organic matters containing at least two active groups, and one or more of single compounds containing crystal water, mixtures of metal oxides and acids, and mixtures of metal hydroxides and acids, wherein each active group is independently selected from amino, carboxyl, hydroxyl, sulfhydryl or acetal group;

the catalyst in the raw material for forming each film layer is independently selected from one or more of organic amine, alcohol amine organic matter, piperazine organic matter, morpholine organic matter, bis (2-dimethylaminoethyl) ether, 1,8 diazabicyclo [5,4,0] undec-7-ene, pyridine organic matter, 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine, phenol organic matter, carboxylate, organic acid, polyalcohol, bismuth-containing organic matter and lead-containing organic matter;

in each of the first base resin grafted with an electron-withdrawing group, the electron-withdrawing group is independently selected from an acid anhydride group, an isocyanate group, a silane coupling group, an acid chloride group, an amino group, a carboxyl group, a hydroxyl group, a mercapto group, a sulfonic group, an epoxy group or a cyano group;

in the first matrix resin grafted with the electron-withdrawing group, the grafting amount of the electron-withdrawing group is 0.1-10 wt%.

2. The co-extrusion film as claimed in claim 1, wherein the first matrix resin grafted with electron-withdrawing groups has a grafting amount of 0.5-3 wt%.

3. The co-extrusion film as claimed in claim 2, wherein the first matrix resin grafted with the electron-withdrawing group has a grafting amount of 0.6-2.8 wt%.

4. The co-extrusion film as claimed in claim 3, wherein the first matrix resin grafted with electron-withdrawing groups has a grafting amount of 1-2.5 wt%.

5. The coextruded film of any of claims 2 to 4 wherein the silane coupling group is a free radical derived from the reaction of an ethylene copolymer with a silane organic.

6. The coextruded film of claim 5 wherein the silane organic is selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-t-butylperoxide silane, vinyltriacetoxysilane, isobutyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, γ -glycidoxypropyltrimethoxysilane or γ -methacryloxypropyltrimethoxysilane.

7. Coextruded film according to claim 1, characterized in that the single compound containing water of crystallization is selected from one or more of calcium disulphate monohydrate, sodium carbonate monohydrate, calcium sulphate dihydrate, copper nitrate trihydrate, copper sulphate pentahydrate, magnesium sulphate hexahydrate, zinc sulphate heptahydrate, sodium carbonate heptahydrate, ferrous sulphate heptahydrate, calcium oxalate monohydrate, calcium oxalate dihydrate, sodium sulphate decahydrate, sodium carbonate decahydrate and aluminium potassium sulphate dodecahydrate.

8. The coextruded film of 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 coextruded film of claim 8 wherein the organic acid is one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlitic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, pyroligneous acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, hentriacontanoic acid, tridecanoic acid, tetracosanoic acid, pentacosanoic acid, and hexacosanoic acid.

10. Coextruded film according to claim 1, characterized in that the organic substance containing two or more reactive groups is selected from one or more of the group of 1,3 propylene glycol, 1, 3-butylene glycol, ethylene diamine, triethanolamine, tetrahydroxypropyl ethylene diamine, maleic acid, fumaric acid, N-methylolacrylamide, N-hydroxyethyl acrylamide and p-hydroxyphenol.

11. Coextruded film according to claim 1, characterized in that the organic amine is selected from one or more of the group consisting of N, N-dimethylbenzylamine, N-dimethylcyclohexylamine, triethylenediamine, N ', N-tetramethylalkylenediamine, N', N-pentamethyldiethylenetriamine, triethylamine, N ', N-dimethylhexadecylamine, N', N-dimethylbutylamine, triethylenediamine;

the alcohol amine organic matter is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N ', N-dimethylethanolamine and N, N' -bis (2-hydroxypropyl) aniline;

the piperazine-based organic compound is one or more selected from the group consisting of 1, 4-dimethylpiperazine, N ', N-diethylpiperazine, N ', N-diethyl-2-methylpiperazine and N ', N-bis- (α -hydroxypropyl) -2-methylpiperazine;

the morpholine organic matter is selected from one or more of the group consisting of N-ethyl morpholine, N-methyl morpholine and N-2-hydroxypropyl dimethyl morpholine;

the pyridine organic matter is selected from one or more of pyridine, N', N-dimethyl pyridine, alkyl pyridine, halogenated pyridine, aminopyridine, methylpyridine, nitropyridine, hydroxypyridine, benzyl pyridine, ethylpyridine and dihydropyridine;

the phenolic organic matter is selected from one or more of the group consisting of 2-methylphenol, 1, 3-benzenediol, 2, 4-dimethylphenol, 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 methylenebis-benzotriazolyl tetramethylbutylphenol;

the carboxylate is selected from one or more of potassium acetate, zinc acetate, calcium acetate and magnesium acetate;

the organic acid is selected from one or more of the group consisting of naphthalene sulfonic acid, toluene sulfonic acid, dodecylbenzene sulfonic acid and trimethyl-N-2-hydroxypropyl hexanoic acid;

the polyol is one or more selected from the group consisting of ethylene glycol, glycerol, trimethylolethane, and pentaerythritol.

12. The co-extrusion film as claimed in any one of claims 1 to 4, wherein the raw materials for forming each film layer further comprise 0 to 99 parts by weight of the second matrix resin, 0 to 5 parts by weight of the crosslinking agent, 0 to 5 parts by weight of the co-crosslinking agent, 0 to 1 part by weight of the light stabilizer, 0 to 2 parts by weight of the ultraviolet light absorber, 0 to 3 parts by weight of the tackifier and 0 to 40 parts by weight of the pigment, respectively and independently.

13. The co-extrusion film as claimed in claim 12, wherein the raw materials forming each of the film layers independently comprise, by weight, 1 to 100 parts of the first base resin grafted with an electron-withdrawing group, 5 to 90 parts of the second base resin, 0.1 to 2 parts of the crosslinking agent, 0.1 to 3 parts of the co-crosslinking agent, 0.1 to 1 part of the light stabilizer, 0.1 to 1 part of the ultraviolet light absorber, 0.1 to 1 part of the tackifier, 0 to 20 parts of the pigment, and 0.1 to 10 parts of the water-generating agent and/or 0.05 to 1 part of the catalyst.

14. The coextruded film of claim 12 wherein the first and second matrix resins of the raw materials forming each film layer are each independently selected from ethylene copolymers or ethylene-alpha-olefin copolymers,

wherein the ethylene copolymer is a copolymer of ethylene and one or more polymerized monomers selected from the group consisting of vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, butadiene, 1, 4-pentadiene, isoprene, ethylidene norbornene, dicyclopentadiene, binary or multicomponent copolymers of 1, 4-hexadiene, polyvinyl butyral, block copolymers of butadiene/isoprene and styrene, natural rubber or trans-polyisoprene rubber;

the ethylene-alpha-olefin copolymer is obtained by polymerizing ethylene and one or more alpha-olefins with 3-20 carbon atoms.

15. Coextruded film according to claim 14, characterized in that the α -olefin is selected from propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-dodecene.

16. A solar cell module comprising a co-extruded film, wherein the co-extruded film is the co-extruded 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 the co-extruded adhesive film of any one of claims 1 to 15.