A high thermal conductivity, high reflection anti-PID adhesive film and its preparation method

Abstract

The present invention belongs to the field of C08K technology, and more specifically relates to a high thermal conductivity, high reflective anti-PID adhesive film and its preparation method. The high thermal conductivity, high reflective anti-PID adhesive film comprises, from top to bottom, a protective layer, an adhesive layer, and a functional layer; the protective layer is made of EVA or hot melt adhesive film material; the high thermal conductivity, high reflective anti-PID adhesive film prepared by the present invention has good thermal conductivity and reflective properties, and has particularly good anti-PID performance, and can inhibit Ca during use. 2+ 、Na + Migrate to the surface of the film, reduce the occurrence of PID phenomenon, thereby preventing discoloration that may occur when the photovoltaic module is used and extending the service life.

Description

Technical Field

[0001] The present invention belongs to the field of C08K technology, and more specifically relates to a high thermal conductivity, high reflectivity anti-PID adhesive film and a preparation method thereof. Background Art

[0002] With the development of photovoltaic modules and the advancement of technology, there are more and more studies on improving the performance of photovoltaic modules. These studies include improving the performance of photovoltaic modules by improving the solar backsheet and optimizing the use of adhesive films in photovoltaic modules in order to improve the anti-PID performance of photovoltaic modules. These studies are currently the focus of researchers.

[0003] A Chinese invention patent application numbered 201610355463.9 discloses an anti-PID polyolefin film for solar cell modules. The disclosed patent describes a PID-resistant polyolefin film prepared by combining polyolefin resin, organic peroxide, co-crosslinking agent, silane coupling agent, UV absorber, and light stabilizer. The disclosed patent describes a soft, heat-resistant, and PID-resistant film prepared through the interaction between the polyolefin resin and the additives. However, the use of the antioxidants and UV absorbers provided in the disclosed patent may result in powdering or oiling, which may affect the film's anti-PID performance and significantly impact photovoltaic modules.

[0004] In addition to improving the film's anti-PID performance, enhancing the film's high reflectivity and high thermal conductivity is also a necessary condition for extending the film's service life. Therefore, inventing a high thermal conductivity, high reflectivity anti-PID film is an important research direction and challenge for researchers at this stage. Summary of the Invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a high thermal conductivity, high reflectivity anti-PID adhesive film, which comprises, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0006] The protective layer is made of EVA or hot melt adhesive film.

[0007] More preferably, the protective layer is made of EVA.

[0008] The raw materials for preparing the functional layer include: resin masterbatch, functional filler, thickener, dispersant, crosslinking agent and antioxidant.

[0009] More preferably, the raw materials for preparing the functional layer also include pigments.

[0010] More preferably, the pigment includes at least one of iron oxide black and copper chromium black.

[0011] More preferably, the pigment is black iron oxide.

[0012] In some preferred embodiments, the functional filler includes at least one of titanium dioxide, glass powder, zinc oxide, aluminum oxide, silicon nitride, and silicon carbide.

[0013] In some preferred embodiments, the weight ratio of the titanium dioxide, glass powder, zinc oxide, and silicon carbide is 1:(0.5-2):(0.1-1):(0.1-1).

[0014] Further preferably, the weight ratio of the titanium dioxide, glass powder, zinc oxide and silicon carbide is 1:2:0.6:0.3.

[0015] More preferably, the particle size of the zinc oxide is 100-800 nm.

[0016] More preferably, the particle size of the zinc oxide is 300-500 nm.

[0017] During the experimental process, the applicant discovered through a large number of creative experimental explorations that by adding titanium dioxide, glass powder and zinc oxide to this system, the anti-PID performance of the film can be greatly improved. In particular, when the weight ratio of titanium dioxide, glass powder, zinc oxide and silicon carbide is 1: (0.5-2): (0.1-1): (0.1-1), it can be ensured that under the high humidity and high heat conditions (60°C, 85% humidity) in the anti-PID test, there is no blackening on the surface after 96 hours of testing. The applicant speculates that the reason for this phenomenon may be that: the interaction between titanium dioxide, glass powder, zinc oxide and silicon nitride can greatly improve the discoloration phenomenon of the film when used in photovoltaic modules, which can be achieved through Na + and Ca 2+ absorption, thereby inhibiting Na + and Ca 2+ The cations migrate to the surface of the film, thereby improving the film's anti-PID performance;

[0018] In addition, the particle size of zinc oxide added to this system is 300-500nm, and its high surface activity can further enhance the compatibility with titanium dioxide and glass powder, reduce the water vapor barrier rate of the prepared film, enhance its water resistance when used in photovoltaic modules, and improve its service life.

[0019] In some preferred embodiments, the titanium dioxide is selected from rutile titanium dioxide and / or anatase titanium dioxide.

[0020] In some preferred embodiments, the glass powder has a particle size of 100-5000 mesh.

[0021] More preferably, the particle size of the glass powder is 3000 mesh.

[0022] After a large number of creative experimental investigations by the applicant, the applicant found that the titanium dioxide used in this system will only show a protective effect on photovoltaic modules and enhance high temperature resistance and stability when rutile titanium dioxide is used. The reason for this phenomenon is that: there are many oxygen vacancies or defect states on the surface of rutile titanium dioxide. These deep energy level defects will adsorb oxygen free radicals in the air. When used in combination with glass powder of appropriate particle size, there will be a strong steric hindrance in the system, which is convenient for the distribution of rutile titanium dioxide in the functional layer. While improving the high temperature resistance of the functional layer material, it also improves the adsorption effect of oxygen free radicals in the air, thereby reducing the damage of oxygen free radicals to the film on the surface of the film, thereby improving its protective effect on photovoltaic modules.

[0023] During the experiment, the applicant found that the functional fillers added to this system may migrate after long-term use, causing the performance of the photovoltaic modules to be affected. In order to solve the migration problem of the functional fillers in this application, the applicant found that adding a specific thickener to this application can improve this phenomenon.

[0024] In some preferred embodiments, the thickener is selected from at least one of an acrylate thickener, a polyether polyurethane thickener, and a biological lipopolysaccharide thickener.

[0025] More preferably, the thickener is a polyether polyurethane thickener.

[0026] In some preferred embodiments, the weight ratio of the dispersant to the thickener is 1:(0.5-3).

[0027] Further preferably, the weight ratio of the dispersant, thickener and antioxidant is 1:(0.5-3):(0.1-0.5).

[0028] More preferably, the dispersant is a silane coupling agent; preferably, the silane coupling agent is 3-aminopropylmethyldimethoxysilane.

[0029] More preferably, the antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine.

[0030] During the experimental process, the applicant conducted a large number of creative experimental explorations and found that the addition of polyether polyurethane thickener in this application will produce thixotropy in the system, increase viscosity, and provide loading sites for titanium dioxide, glass powder, zinc oxide, and silicon carbide in the system. In addition, in the presence of 3-aminopropylmethyldimethoxysilane, it will interact with the polyether polyurethane thickener, avoiding the coagulation problem caused by the high surface activity of the particles. In addition, the presence of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine added to this system will cause the existing benzene rings and hydroxyl groups to produce an electronic conjugation effect when exposed to sunlight, thereby reducing the influence of steric hindrance, thereby enhancing the capture of oxygen free radicals, and avoiding the migration of titanium dioxide, glass powder, zinc oxide, and silicon carbide that may occur in the film as the use time increases.

[0031] Moreover, due to the addition of polyether polyurethane thickener, in the presence of titanium dioxide, glass powder, zinc oxide, and silicon carbide, the film can form a microscopic rough surface after curing, which can reflect light multiple times and enhance its reflective effect.

[0032] In some preferred embodiments, the raw materials for preparing the functional layer include, by weight, 0.1-3 parts of pigment, 30-40 parts of functional filler, 1-5 parts of dispersant, 1-5 parts of thickener, 0.1-3 parts of crosslinking agent, 0.05-1 part of antioxidant, and 80-150 parts of resin masterbatch.

[0033] In some preferred embodiments, the resin masterbatch includes EVA masterbatch and / or polyolefin masterbatch.

[0034] More preferably, the resin masterbatch is EVA masterbatch.

[0035] Further preferably, the adhesive layer is a hot melt adhesive film material.

[0036] In some preferred embodiments, the crosslinking agent is a peroxide crosslinking agent.

[0037] Further preferably, the peroxide crosslinking agent includes benzoyl peroxide.

[0038] In the present application, the hot melt adhesive film material is not particularly limited, as long as it can achieve adhesive film bonding.

[0039] A second aspect of the present invention provides a method for preparing a high thermal conductivity, high reflectivity anti-PID film, comprising the following steps:

[0040] 1) Preparation of protective layer;

[0041] 2) Preparation of functional layer;

[0042] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0043] Preferably, the method for preparing the protective layer comprises the following steps:

[0044] The EVA is extruded in a twin-screw extruder to obtain a sheet for use.

[0045] Preferably, the method for preparing the functional layer comprises the following steps:

[0046] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the other ingredients except the resin masterbatch into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 80-100℃, cast them into a film, and then perform pre-crosslinking treatment to obtain the product.

[0047] A third aspect of the present invention provides a photovoltaic module comprising the aforementioned high thermal conductivity, high reflectivity anti-PID adhesive film.

[0048] Beneficial effects: The high thermal conductivity and high reflectivity anti-PID film prepared by the present invention has the following advantages over the prior art:

[0049] The high thermal conductivity and high reflective anti-PID film prepared by the present invention has good thermal conductivity and reflective properties, and has a particularly good anti-PID performance, which can inhibit the Ca 2+ 、Na + It migrates to the surface of the film, reducing the occurrence of PID, thereby preventing discoloration that may occur when the photovoltaic module is used, extending its service life, and having a better reflective effect under the irradiation of 380-750nm sunlight, ensuring that the diffuse reflectivity reaches more than 85%. DETAILED DESCRIPTION

[0050] Example

[0051] Example 1

[0052] A high thermal conductivity, high reflectivity anti-PID film, comprising, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0053] The material of the protective layer is EVA, which is extruded through a twin-screw extruder to obtain a sheet for standby use;

[0054] The adhesive layer is a hot melt adhesive film;

[0055] The raw materials for preparing the functional layer include, by weight, 0.5 parts of pigment, 39 parts of functional filler, 1.5 parts of dispersant, 2.4 parts of thickener, 0.8 parts of crosslinking agent, 0.6 parts of antioxidant, and 100 parts of resin masterbatch.

[0056] The functional filler includes titanium dioxide, glass powder, zinc oxide, and silicon carbide in a weight ratio of 1:2:0.6:0.3;

[0057] The titanium dioxide is rutile titanium dioxide;

[0058] The glass powder has a particle size of 3000 mesh, model: 8886, purchased from Foshan Jinggu Material Technology Co., Ltd.

[0059] The zinc oxide has an average particle size of 400 nm, model XT-ZNO-04, and was purchased from Shanghai Xiangtian Nanomaterials Co., Ltd.

[0060] The dispersant is 3-aminopropylmethyldimethoxysilane;

[0061] The thickener is a polyether polyurethane thickener, model PUR2150, purchased from Guangzhou Houhuan Chemical Additive Co., Ltd.

[0062] The cross-linking agent is benzoyl oxide;

[0063] The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine;

[0064] The resin masterbatch is EVA masterbatch, purchased from Dongguan Jinsuyan Plastic Technology Co., Ltd.;

[0065] The pigment is black iron oxide.

[0066] A method for preparing a high thermal conductivity and high reflectivity anti-PID film comprises the following steps:

[0067] 1) Preparation of protective layer;

[0068] 2) Preparation of functional layer;

[0069] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0070] The method for preparing the functional layer comprises the following steps:

[0071] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the pigment, functional filler, dispersant, thickener, and antioxidant into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 90°C, cast them into a film, and then add a cross-linking agent for pre-cross-linking treatment to obtain the product.

[0072] Example 2

[0073] A high thermal conductivity, high reflectivity anti-PID film, comprising, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0074] The material of the protective layer is EVA, which is extruded through a twin-screw extruder to obtain a sheet for standby use;

[0075] The adhesive layer is a hot melt adhesive film;

[0076] The raw materials for preparing the functional layer include, by weight, 0.5 parts of pigment, 39 parts of functional filler, 1.5 parts of dispersant, 2.4 parts of thickener, 0.8 parts of crosslinking agent, 0.6 parts of antioxidant, and 100 parts of resin masterbatch.

[0077] The functional filler includes titanium dioxide, glass powder, zinc oxide, and silicon carbide in a weight ratio of 1:2:0.6:0.3;

[0078] The titanium dioxide is anatase titanium dioxide;

[0079] The glass powder has a particle size of 3000 mesh, model: 8886, purchased from Foshan Jinggu Material Technology Co., Ltd.

[0080] The zinc oxide has an average particle size of 5 μm, model XT-ZNO-07, and was purchased from Shanghai Xiangtian Nanomaterials Co., Ltd.

[0081] The dispersant is 3-aminopropylmethyldimethoxysilane;

[0082] The thickener is a polyether polyurethane thickener, model PUR2150, purchased from Guangzhou Houhuan Chemical Additive Co., Ltd.

[0083] The cross-linking agent is benzoyl oxide;

[0084] The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine;

[0085] The resin masterbatch is EVA masterbatch, purchased from Dongguan Jinsuyan Plastic Technology Co., Ltd.;

[0086] The pigment is black iron oxide.

[0087] A method for preparing a high thermal conductivity and high reflectivity anti-PID film comprises the following steps:

[0088] 1) Preparation of protective layer;

[0089] 2) Preparation of functional layer;

[0090] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0091] The method for preparing the functional layer comprises the following steps:

[0092] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the pigment, functional filler, dispersant, thickener, and antioxidant into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 90°C, cast them into a film, and then add a cross-linking agent for pre-cross-linking treatment to obtain the product.

[0093] Example 3

[0094] A high thermal conductivity, high reflectivity anti-PID film, comprising, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0095] The material of the protective layer is EVA, which is extruded through a twin-screw extruder to obtain a sheet for standby use;

[0096] The adhesive layer is a hot melt adhesive film;

[0097] The raw materials for preparing the functional layer include, by weight, 0.5 parts of pigment, 39 parts of functional filler, 1.5 parts of dispersant, 2.4 parts of thickener, 0.8 parts of crosslinking agent, 0.6 parts of antioxidant, and 100 parts of resin masterbatch.

[0098] The functional filler includes titanium dioxide;

[0099] The titanium dioxide is rutile titanium dioxide;

[0100] The dispersant is 3-aminopropylmethyldimethoxysilane;

[0101] The thickener is a polyether polyurethane thickener, model PUR2150, purchased from Guangzhou Houhuan Chemical Additive Co., Ltd.

[0102] The cross-linking agent is benzoyl oxide;

[0103] The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine;

[0104] The resin masterbatch is EVA masterbatch, purchased from Dongguan Jinsuyan Plastic Technology Co., Ltd.;

[0105] The pigment is black iron oxide.

[0106] A method for preparing a high thermal conductivity and high reflectivity anti-PID film comprises the following steps:

[0107] 1) Preparation of protective layer;

[0108] 2) Preparation of functional layer;

[0109] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0110] The method for preparing the functional layer comprises the following steps:

[0111] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the pigment, functional filler, dispersant, thickener, and antioxidant into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 90°C, cast them into a film, and then add a cross-linking agent for pre-cross-linking treatment to obtain the product.

[0112] Example 4

[0113] A high thermal conductivity, high reflectivity anti-PID film, comprising, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0114] The material of the protective layer is EVA, which is extruded through a twin-screw extruder to obtain a sheet for standby use;

[0115] The adhesive layer is a hot melt adhesive film;

[0116] The raw materials for preparing the functional layer include, by weight, 0.5 parts of pigment, 39 parts of functional filler, 1.5 parts of dispersant, 2.4 parts of thickener, 0.8 parts of crosslinking agent, 0.6 parts of antioxidant, and 100 parts of resin masterbatch.

[0117] The functional filler includes titanium dioxide, glass powder, zinc oxide, and silicon carbide in a weight ratio of 1:2:0.6:0.3;

[0118] The titanium dioxide is rutile titanium dioxide;

[0119] The glass powder has a particle size of 3000 mesh, model: 8886, purchased from Foshan Jinggu Material Technology Co., Ltd.

[0120] The zinc oxide has an average particle size of 400 nm, model XT-ZNO-04, and was purchased from Shanghai Xiangtian Nanomaterials Co., Ltd.

[0121] The dispersant is 3-aminopropylmethyldimethoxysilane;

[0122] The thickener is sodium carboxymethyl cellulose, purchased from Jinan Yuncheng Biotechnology Co., Ltd.

[0123] The cross-linking agent is benzoyl oxide;

[0124] The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine;

[0125] The resin masterbatch is EVA masterbatch, purchased from Dongguan Jinsuyan Plastic Technology Co., Ltd.;

[0126] The pigment is black iron oxide.

[0127] A method for preparing a high thermal conductivity and high reflectivity anti-PID film comprises the following steps:

[0128] 1) Preparation of protective layer;

[0129] 2) Preparation of functional layer;

[0130] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0131] The method for preparing the functional layer comprises the following steps:

[0132] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the pigment, functional filler, dispersant, thickener, and antioxidant into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 90°C, cast them into a film, and then add a cross-linking agent for pre-cross-linking treatment to obtain the product.

[0133] Example 5

[0134] A high thermal conductivity, high reflectivity anti-PID film, comprising, from top to bottom, a protective layer, an adhesive layer, and a functional layer;

[0135] The material of the protective layer is EVA, which is extruded through a twin-screw extruder to obtain a sheet for standby use;

[0136] The adhesive layer is a hot melt adhesive film;

[0137] The raw materials for preparing the functional layer include, by weight, 0.5 parts of pigment, 39 parts of functional filler, 1.5 parts of dispersant, 2.4 parts of thickener, 0.8 parts of crosslinking agent, 0.6 parts of antioxidant, and 100 parts of resin masterbatch.

[0138] The functional filler includes titanium dioxide, zinc oxide, and silicon carbide in a weight ratio of 1:0.6:0.3;

[0139] The titanium dioxide is rutile titanium dioxide;

[0140] The zinc oxide has an average particle size of 400 nm, model XT-ZNO-04, and was purchased from Shanghai Xiangtian Nanomaterials Co., Ltd.

[0141] The dispersant is 3-aminopropylmethyldimethoxysilane;

[0142] The thickener is a polyether polyurethane thickener, model PUR2150, purchased from Guangzhou Houhuan Chemical Additive Co., Ltd.

[0143] The cross-linking agent is benzoyl oxide;

[0144] The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine;

[0145] The resin masterbatch is EVA masterbatch, purchased from Dongguan Jinsuyan Plastic Technology Co., Ltd.;

[0146] The pigment is black iron oxide.

[0147] A method for preparing a high thermal conductivity and high reflectivity anti-PID film comprises the following steps:

[0148] 1) Preparation of protective layer;

[0149] 2) Preparation of functional layer;

[0150] 3) Bonding the protective layer and the functional layer together through the adhesive layer.

[0151] The method for preparing the functional layer comprises the following steps:

[0152] First, add the resin masterbatch into the twin-screw extruder and melt it. Then, add the pigment, functional filler, dispersant, thickener, and antioxidant into the reaction twin-screw through the side. In the twin-screw reaction extruder, further mix them evenly, melt them, extrude them at 90°C, cast them into a film, and then add a cross-linking agent for pre-cross-linking treatment to obtain the product.

[0153] Performance testing:

[0154] 1. PID test: The films prepared in Examples 1-5 were used to prepare solar cell modules, wherein the upper layer was a glass substrate, the middle layer was a cell, and the lower layer was a backsheet. The functional layer of the film prepared in this application was adjacent to the glass substrate. The specific preparation method is not particularly limited. After the module was prepared, a conductive film was coated around the edge of the module.

[0155] The prepared battery assembly was placed under conditions of 60° C. and 85% humidity. After 96 hours, the assembly power attenuation rate was recorded and the results are recorded in the table below.

[0156] 2. Reflectivity: Test the reflectivity of the product under 380-750nm wavelength light according to the IEC-62805-2 test standard and record the results in the table below.

[0157]

Claims

1. A high thermal conductivity, high reflectivity anti-PID film, characterized in that: From top to bottom, it includes: protective layer, adhesive layer, functional layer; The protective layer is made of EVA or hot melt adhesive film. The raw materials for preparing the functional layer include: resin masterbatch, functional filler, thickener, dispersant, crosslinking agent, and antioxidant; The functional filler includes titanium dioxide, glass powder, zinc oxide, and silicon carbide; The weight ratio of titanium dioxide, glass powder, zinc oxide and silicon carbide is 1: (0.5-2): (0.1-1): (0.1-1); The thickener is a polyether polyurethane thickener; The titanium dioxide is rutile titanium dioxide; The average particle size of the zinc oxide is 400 nm.

2. The high thermal conductivity and high reflectivity anti-PID film according to claim 1, characterized in that: The particle size of the glass powder is 100-5000nm.

3. The high thermal conductivity and high reflectivity anti-PID film according to claim 1, characterized in that: The weight ratio of the dispersant to the thickener is 1:(0.5-3).

4. The high thermal conductivity and high reflectivity anti-PID film according to claim 1, characterized in that: The resin masterbatch includes EVA masterbatch and / or polyolefin masterbatch.

5. A method for preparing a high thermal conductivity, high reflectivity anti-PID film according to any one of claims 1 to 4, characterized in that: The following steps are involved: 1) Preparation of protective layer; 2) Preparation of functional layer; 3) The protective layer and the functional layer are bonded together through the bonding layer.

6. A photovoltaic module, characterized in that: The invention comprises the high thermal conductivity, high reflective anti-PID adhesive film according to any one of claims 1 to 4.

Images