Anti-slip POE (Polyolefin Elastomer) packaging adhesive film capable of resisting precipitation of auxiliaries and preparation method thereof

Abstract

The invention belongs to the technical field of photovoltaic packaging adhesive films, and particularly relates to an assistant precipitation resistant anti-slip POE packaging adhesive film and a preparation method thereof, and the preparation method comprises the following steps: S1, mixing raw materials, and uniformly stirring to obtain a micro-foaming layer raw material and a skeleton layer raw material; s2, performing melt extrusion, namely performing melt extrusion on the raw materials of the framework layer through a single-screw extruder, and controlling the extrusion temperature and the screw rotating speed to obtain the framework layer; s3, supercritical fluid micro-foaming extrusion is conducted, specifically, raw materials of a micro-foaming layer are subjected to melt extrusion through a co-rotating twin-screw extruder, the extrusion temperature and the screw rotating speed are controlled, supercritical fluid carbon dioxide is introduced in the extrusion process to serve as a foaming agent, then heating foaming is conducted, the adding amount of the foaming agent is 0.5%-2% of the mass of matrix resin, the foaming temperature is 160-200 DEG C, the foaming pressure is 10-20 MPa, and the foaming layer is obtained; a micro-foaming layer is obtained; and S4, tape casting: carrying out three-layer co-extrusion on the micro-foaming layer, the skeleton layer and the micro-foaming layer to form an ABA structural adhesive film, thereby obtaining the POE packaging adhesive film.

Description

Technical Field

[0001] The present invention belongs to the technical field of photovoltaic encapsulation films, and particularly relates to an anti-skid POE encapsulation film that resists precipitation of auxiliary agents and a preparation method thereof. Background Art

[0002] Currently, the main encapsulation materials on the market include transparent EVA film, white EVA film, polyolefin (POE) film, co-extruded polyolefin composite film (EPE) (EVA-POE-EVA) film, and other encapsulation films (including PDMS / Silicon film, PVB film, and TPU film). POE materials, owing to their higher water vapor barrier, improved weather resistance, and superior resistance to PID (potential-induced degradation), have garnered widespread attention and become a research hotspot in recent years. The offshore photovoltaic market, in particular, is expected to grow rapidly with technological advancements and cost reductions. Global offshore photovoltaic installed capacity is projected to increase significantly by 2030, particularly in Europe and China, where related projects are gradually being implemented. By 2024, some Chinese companies will have completed pilot production of POE particles, and new production capacity is steadily increasing. The current local supply rate is 6.2%. New production capacity is expected to be operational by 2025, with more companies entering mass production, further increasing the local supply rate.

[0003] However, POE material films are prone to slipping during the lamination process of photovoltaic modules. Therefore, how to avoid the film slipping during the production of client modules is a technical problem that urgently needs to be solved in this field.

[0004] It should be noted that the above information disclosed in this background technology section is only used to understand the background technology of the present application concept, and therefore, the above description is not considered to constitute information of the prior art. Summary of the Invention

[0005] The embodiments of the present disclosure at least provide an anti-skid POE encapsulation film that resists precipitation of auxiliary agents and a preparation method thereof.

[0006] In the first aspect, the embodiment of the present disclosure provides a preparation method of a POE encapsulation film, comprising the following steps: S1, raw material mixing, mixing and stirring the base resin, anti-aging agent, processing aid and anti-acid aid of the micro-foam layer to obtain the raw material of the micro-foam layer, and mixing and stirring the base resin, cross-linking agent, auxiliary cross-linking agent and tackifier of the skeleton layer to obtain the raw material of the skeleton layer; S2, melt extrusion, melt-extrude the raw material of the skeleton layer through a single-screw extruder, control the extrusion temperature and screw speed to obtain the skeleton layer; S3, supercritical fluid micro-foam extrusion, and melt-extrude the raw material of the micro-foam layer through a single-screw extruder. A co-rotating twin-screw extruder performs melt extrusion, controls the extrusion temperature and screw speed, and introduces supercritical fluid carbon dioxide as a foaming agent during the extrusion process. The temperature is then increased for foaming. The amount of the foaming agent added is 0.5% to 2% of the mass of the matrix resin. The foaming temperature is 160 to 200°C, and the foaming pressure is 10 to 20 MPa to obtain a micro-foam layer. S4, cast molding, forms an ABA structural adhesive film by three-layer co-extrusion of the micro-foam layer, the skeleton layer, and the micro-foam layer. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a POE encapsulation adhesive film is obtained.

[0007] In an optional embodiment, the base resin includes any one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, hyperbranched polyolefin elastomer, vinyl polyolefin elastomer, and ultra-low density polyethylene.

[0008] In an optional embodiment, the anti-aging aid includes any one or more combinations of antioxidants, light stabilizers, and ultraviolet absorbers; wherein the antioxidant includes any one or more combinations of hindered amine antioxidants, phosphite antioxidants, and thioester antioxidants; the light stabilizer is a hindered amine light stabilizer, including any one or a combination of two of dimethyl piperidine derivatives and disubstituted piperidine derivatives; the ultraviolet absorber includes any one or more combinations of benzotriazole light stabilizers, benzophenones, substituted acrylonitriles, triazines, salicylates, naphthotriazoles, phenols, and amides.

[0009] In an optional embodiment, the processing aid includes any one or more combinations of paraffin wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate wax, erucamide, and oleamide.

[0010] In an optional embodiment, the antacid auxiliary agent includes any one or more combinations of zinc oxide, aluminum oxide, magnesium oxide, calcium oxide, and potassium oxide.

[0011] In an optional embodiment, the cross-linking agent includes any one or more combinations of dicumyl peroxide, tert-butyl peroxide, tert-butylacetyl peroxide, tert-butyl carbonate peroxide, tert-butyl perbenzoate, tert-butyl peroxypivalate, and tert-butyl peroxy-3,5,5-trimethylhexanoate.

[0012] In an optional embodiment, the auxiliary cross-linking agent includes any one or more combinations of triallyl isocyanate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, and ditrimethylolpropane tetraacrylate.

[0013] In an optional embodiment, the adhesion promoter includes any one or more combinations of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0014] In an optional embodiment, in step S1, the mixing and stirring temperature of the raw materials for the micro-foam layer is 25-35° C., and the stirring time is 1-2 hours; the mixing and stirring temperature of the raw materials for the skeleton layer is 38-42° C., and the stirring time is 1-15 hours.

[0015] In an optional embodiment, the screw diameter of the single-screw extruder in step S2 is any one of 150 mm, 160 mm, 180 mm, 200 mm, 220 mm, and 240 mm, the screw aspect ratio is any one between 20:1 and 40:1, the extrusion temperature is 70 to 110°C, and the screw speed is 30 to 50 rpm.

[0016] In an optional embodiment, the screw diameter of the co-rotating twin-screw extruder in step S3 is any one of 65 mm, 75 mm, 95 mm, 110 mm, and 135 mm, the screw aspect ratio is any one between 32:1 and 56:1, the extrusion temperature is 70 to 110°C, and the screw speed is 100 to 200 rpm.

[0017] In the second aspect, the embodiment of the present disclosure also provides a POE encapsulation film, which is prepared by the method as described above, including: a micro-foam layer, a skeleton layer and a micro-foam layer stacked and co-extruded in sequence, with a thickness ratio ranging from 1:1:1 to 1:9:1; the porosity of the micro-foam layer is 15% to 30%, and the pore diameter is 5μm to 80μm.

[0018] In an optional embodiment, the POE packaging film has a gram weight range of 50 g / ㎡ to 500 g / ㎡.

[0019] In a third aspect, an embodiment of the present disclosure further provides a photovoltaic module comprising the POE encapsulation film as described above.

[0020] The beneficial effect of the present invention is that the anti-slip POE encapsulation film with anti-additive precipitation and its preparation method adopt a supercritical fluid micro-foaming process to make the film have a uniform microporous structure. The physical foaming method can not only form effective physical adsorption of the surface additive, provide the surface roughness of the film while enhancing the anti-slip ability, but also further optimize the dispersion and distribution of each additive in the matrix resin through the heterogeneous nucleation effect. In addition, the optimized preparation process does not require the introduction of chemical additives for foaming, the production process is more environmentally friendly, and will not affect the performance of other inorganic additives.

[0021] Other features and advantages of the present invention will be described in the following description, and in part will become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures particularly pointed out in the description.

[0022] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail as follows. DETAILED DESCRIPTION

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0024] As used herein, the phrases "in one embodiment," "according to one embodiment," "in some embodiments," and the like generally refer to the fact that the particular feature, structure, or characteristic following the phrase may be included in at least one embodiment of the present disclosure. Thus, a particular feature, structure, or characteristic may be included in more than one embodiment of the present disclosure, such that these phrases do not necessarily refer to the same embodiment. As used herein, the terms "example," "exemplary," and the like are used to "serve as an example, instance, or illustration." Any implementation, aspect, or design described herein as "example" or "exemplary" is not necessarily to be construed as preferred or advantageous over other implementations, aspects, or designs. Instead, the use of the terms "example," "exemplary," and the like is intended to present concepts in a concrete manner.

[0025] As used herein, expressions such as “at least one of,” when following a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, the expression “at least one of a, b, and c” should be understood to include only a, only b, only c, both a and b, both a and c, both b and c, or all of a, b, and c.

[0026] The terms used herein are only used to describe specific exemplary configurations and are not intended to be limiting. As used herein, the singular articles "a", "an" and "the" may also be intended to include plural forms, unless otherwise clearly indicated herein. The terms "comprise", "include" and "have" are inclusive and therefore specify the presence of features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or combinations thereof. The method steps, processes and operations described herein should not be interpreted as necessarily requiring them to be performed in the particular order discussed or shown, unless specifically identified as an execution order. Additional or alternative steps may be adopted.

[0027] POE materials still face significant technical difficulties in practical applications. Due to the non-polarity of POE, it has poor compatibility with polar additives (such as cross-linking agents, co-cross-linking agents, tackifiers, etc.) added during the film preparation process. This makes it difficult for the additives to be completely absorbed during the single-screw cast extrusion process. After the POE film is cooled and formed, the additives slowly migrate to the surface of the film, resulting in problems such as film slippage and short shelf life during the production of client components. At the same time, the migrated additives will also cause the surface of the POE film to be over-cross-linked during the lamination process, affecting the aging adhesion with the glass, causing water vapor to invade from all sides and reducing the aging reliability of the component.

[0028] The defects in the above solutions are the results obtained by the inventors after practice and careful research. Therefore, the process of discovering the above problems and the solutions proposed by this disclosure for the above problems below should be the contributions made by the inventors to this disclosure during the disclosure process.

[0029] The following are some embodiments of the present invention described in detail. In the absence of conflict, the following embodiments and features in the embodiments can be combined with each other.

[0030] The embodiment of the present disclosure provides a preparation method of a POE encapsulation film, comprising the following steps: S1, mixing raw materials, mixing and stirring the base resin, anti-aging agent, processing aid and anti-acid aid of the micro-foam layer to obtain the raw material of the micro-foam layer, and mixing and stirring the base resin, cross-linking agent, auxiliary cross-linking agent and tackifier of the skeleton layer to obtain the raw material of the skeleton layer; S2, melt extrusion, melt-extrude the raw material of the skeleton layer through a single-screw extruder, controlling the extrusion temperature and screw speed to obtain the skeleton layer; S3, supercritical fluid micro-foam extrusion, extruding the raw material of the micro-foam layer through a co-rotating double-screw extruder, and extruding the raw material of the skeleton layer. The screw extruder performs melt extrusion, controls the extrusion temperature and screw speed, and introduces supercritical fluid carbon dioxide as a foaming agent during the extrusion process, and then heats up for foaming. The amount of the foaming agent added is 0.5% to 2% of the mass of the matrix resin, the foaming temperature is 160 to 200°C, and the foaming pressure is 10 to 20 MPa to obtain a micro-foam layer; S4, cast molding, forms an ABA structural film by three-layer co-extrusion of the micro-foam layer, the skeleton layer, and the micro-foam layer, and then undergoes casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding to obtain a POE encapsulation film.

[0031] Specifically, in the micro-foamed layer, due to the small particle size of anti-aging agents, processing aids, anti-acid additives, etc., they can form a more uniform dispersion system in the matrix resin POE after twin-screw micro-foaming. The tiny particle size of these additives can not only significantly increase their specific surface area in the matrix resin, but also further optimize their dispersion and distribution in the matrix resin through the heterogeneous nucleation effect. Specifically, the heterogeneous nucleation effect can enable these additives to form a more stable dispersed phase in the POE matrix, thereby effectively improving the uniformity and stability of the additives in the matrix resin. In addition, this layer is designed to form effective physical adsorption on the migrating additives through the micro-foamed pores inside the POE, effectively reducing the migration of the additives to the surface of the film, improving the surface roughness of the film, and thus enhancing the anti-slip performance of the POE film. At the same time, this optimized dispersion state can not only fully exert the effectiveness of the additives, such as the weather resistance of anti-aging agents, the fluidity optimization of processing additives, and the adaptability of anti-acid additives to acidic environments, but also further improve the overall performance of the composite material, including mechanical properties, moisture and heat resistance, and processing performance. Through this synergistic effect, not only can the POE film's ability to resist additive precipitation and slippage be improved, but also the comprehensive anti-aging performance of the POE film at the component end is improved. Secondly, the foaming process is changed to physical foaming, without the introduction of other chemical additives, which does not affect the uniform dispersion and thermal stability of the added inorganic substances. The production process is environmentally friendly and the foaming process is green and pollution-free.

[0032] Specifically, in the skeleton layer, this layer is mainly composed of a base resin and a cross-linking agent, a co-cross-linking agent, a tackifier, etc. It is a crucial layer in the POE film structure, mainly playing a supporting role, significantly improving the overall strength and bonding performance of the film. During the lamination process, this layer can not only carry the cross-linking agent and the co-cross-linking agent, but also significantly enhance the bonding performance between the film and the glass surface through the introduction of the tackifier, thereby ensuring the reliability and durability of the laminated assembly. At the same time, the structural design of the skeleton layer can effectively support the performance of the micro-foam layer of the edge layer, so that it remains stable during the lamination process and gives full play to the excellent performance of the micro-foam layer. This synergistic effect can not only significantly improve the mechanical properties, durability and processing performance of the POE film, but also ensure the long-term stability and reliability of the film in complex environments, providing a solid guarantee for the performance of the entire assembly.

[0033] Specifically, the ABA three-layer functional layer design effectively reduces the migration of additives. The application of supercritical fluid micro-foaming technology gives the film a uniform microporous structure, improving the anti-additive precipitation and anti-slip properties of the POE encapsulation film. At the same time, the green preparation process of physical foaming technology reduces energy consumption and environmental pollution, meeting the requirements of sustainable development.

[0034] In some embodiments, specifically, the matrix resin includes any one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, hyperbranched polyolefin elastomer, vinyl polyolefin elastomer, and ultra-low density polyethylene; preferably, the matrix resin is ethylene-butene copolymer or ethylene-octene copolymer.

[0035] In some embodiments, specifically, the anti-aging aid includes any one or more combinations of antioxidants, light stabilizers, and ultraviolet absorbers; wherein the antioxidant includes any one or more combinations of hindered amine antioxidants, phosphite antioxidants, and thioester antioxidants; the light stabilizer is a hindered amine light stabilizer, including any one or a combination of two of dimethyl piperidine derivatives and disubstituted piperidine derivatives; the ultraviolet absorber includes any one or more combinations of benzotriazole light stabilizers, benzophenones, substituted acrylonitriles, triazines, salicylates, naphthotriazoles, phenols, and amides.

[0036] In some embodiments, specifically, the processing aid includes any one or more combinations of paraffin wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate wax, erucamide, and oleamide; preferably, the processing aid is any one or more of polyethylene wax and erucamide.

[0037] In some embodiments, specifically, the antacid aid includes any one or more combinations of zinc oxide, aluminum oxide, magnesium oxide, calcium oxide, and potassium oxide; preferably, the antacid aid is any one or more of magnesium oxide and aluminum oxide.

[0038] In some embodiments, specifically, the cross-linking agent includes any one or more combinations of dicumyl peroxide, tert-butyl peroxide, tert-butyl acetyl peroxide, tert-butyl carbonate peroxide, tert-butyl perbenzoate, tert-butyl peroxypivalate, and tert-butyl peroxy-3,5,5-trimethylhexanoate; preferably, the cross-linking agent is any one or more of tert-butyl peroxide, tert-butyl acetyl peroxide, and tert-butyl peroxy-3,5,5-trimethylhexanoate.

[0039] In some embodiments, specifically, the auxiliary cross-linking agent includes any one or more combinations of triallyl isocyanate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, and ditrimethylolpropane tetraacrylate; preferably, the auxiliary cross-linking agent is any one or more of triallyl isocyanate and trimethylolpropane triacrylate.

[0040] In some embodiments, specifically, the adhesion promoter includes any one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane; the adhesion promoter is any one or more of γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane.

[0041] In some embodiments, specifically, in step S1, the mixing and stirring temperature of the raw materials for the micro-foam layer is 25-35° C., and the stirring time is 1-2 hours; the mixing and stirring temperature of the raw materials for the skeleton layer is 38-42° C., and the stirring time is 1-15 hours.

[0042] Preferably, the mixing temperature of the edge micro-foam layer formula in step S1 is 25° C. and the stirring time is 1 hour; the mixing temperature of the middle skeleton layer formula is 38° C. and the stirring time is 12 hours.

[0043] In some embodiments, specifically, the screw diameter of the single-screw extruder in step S2 is any one of 150 mm, 160 mm, 180 mm, 200 mm, 220 mm, and 240 mm, the screw aspect ratio is any one between 20:1 and 40:1, the extrusion temperature is 70 to 110°C, and the screw speed is 30 to 50 rpm.

[0044] Preferably, the diameter of the single-screw extruder in step S2 is 160 mm or 180 mm, the screw aspect ratio is 35:1, the extrusion temperature is 75° C. to 85° C., and the screw speed is 35 rpm.

[0045] In some embodiments, specifically, the screw diameter of the co-rotating twin-screw extruder in step S3 is any one of 65 mm, 75 mm, 95 mm, 110 mm, and 135 mm, the screw aspect ratio is any one between 32:1 and 56:1, the extrusion temperature is 70 to 110° C., and the screw speed is 100 to 200 rpm.

[0046] Preferably, the screw diameter of the co-rotating twin-screw extruder in step 3 is 110 mm or 135 mm, the screw aspect ratio is 44:1 or 56:1, the extrusion temperature is 75°C to 95°C, and the screw speed is 450 rpm. Supercritical fluid microfoaming: Supercritical fluid carbon dioxide is introduced as a foaming agent during the extrusion process. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of 15% to 30% and a pore size of 5 μm to 80 μm during the screw extrusion process. The amount of foaming agent added is 0.15% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 15 MPa.

[0047] Preferably, the distributor involved in step S4 is a three-layer swing blade distributor, and the mold is an outer membrane composite mold, wherein the distributor and the mold are respectively equipped with mold temperature controllers for separate temperature control, the temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C.

[0048] The embodiment of the present disclosure also provides a POE encapsulation film, which is prepared by the method as described above, including: a micro-foam layer, a skeleton layer and a micro-foam layer stacked and co-extruded in sequence, with a thickness ratio ranging from 1:1:1 to 1:9:1; the porosity of the micro-foam layer is 15% to 30%, and the pore diameter is 5μm to 80μm.

[0049] In some embodiments, specifically, the POE packaging film has a gram weight range of 50 g / ㎡ to 500 g / ㎡.

[0050] The embodiment of the present disclosure further provides a photovoltaic module, comprising the POE encapsulation film as described above.

[0051] Example 1:

[0052] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0053] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0054] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0055] The specific preparation process steps are as follows:

[0056] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0057] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0058] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.5% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 15MPa.

[0059] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0060] Example 2:

[0061] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0062] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0063] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0064] The specific preparation process steps are as follows:

[0065] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0066] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0067] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.5% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 13MPa.

[0068] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0069] Example 3:

[0070] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0071] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0072] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0073] The specific preparation process steps are as follows:

[0074] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0075] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0076] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.5% of the resin mass. The foaming temperature is 175°C and the foaming pressure is 11MPa.

[0077] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0078] Example 4:

[0079] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0080] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0081] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0082] The specific preparation process steps are as follows:

[0083] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0084] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0085] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.5% of the resin mass. The foaming temperature is 175°C and the foaming pressure is 9MPa.

[0086] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0087] Example 5:

[0088] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0089] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0090] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0091] The specific preparation process steps are as follows:

[0092] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0093] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0094] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.2% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 15MPa.

[0095] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0096] Example 6:

[0097] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0098] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0099] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0100] The specific preparation process steps are as follows:

[0101] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0102] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0103] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The foaming agent is added at a rate of 1.0% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 13MPa.

[0104] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0105] Example 7:

[0106] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0107] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0108] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0109] The specific preparation process steps are as follows:

[0110] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0111] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0112] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 0.8% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 11MPa.

[0113] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0114] Example 8:

[0115] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0116] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0117] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0118] The specific preparation process steps are as follows:

[0119] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0120] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0121] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 0.6% of the resin mass, the foaming temperature is 175°C, and the foaming pressure is 9MPa.

[0122] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0123] Example 9:

[0124] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0125] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0126] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0127] The specific preparation process steps are as follows:

[0128] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0129] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0130] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.2% of the resin mass, the foaming temperature is 155°C, and the foaming pressure is 15MPa.

[0131] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0132] Example 10:

[0133] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0134] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0135] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0136] The specific preparation process steps are as follows:

[0137] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0138] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0139] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 1.0% of the resin mass, the foaming temperature is 155°C, and the foaming pressure is 13MPa.

[0140] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0141] Example 11:

[0142] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0143] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0144] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0145] The specific preparation process steps are as follows:

[0146] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0147] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0148] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 0.8% of the resin mass, the foaming temperature is 155°C, and the foaming pressure is 11MPa.

[0149] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0150] Example 12:

[0151] A non-slip POE encapsulating film with an anti-adjuvant precipitation and an environmentally friendly preparation process thereof. The raw materials of the three-layer structure of the non-slip POE encapsulating film with an anti-adjuvant precipitation include, by weight:

[0152] Edge layer A (micro-foam layer): 100 parts of ethylene-octene copolymer (ENGAGE PV 8660), 0.5 parts of hindered amine light stabilizer (UV-770), 0.5 parts of ultraviolet absorber (UV-531), 0.5 parts of processing aid erucamide (Crodamide212), 0.5 parts of anti-acid additive aluminum oxide ( M632SP) 0.5 parts.

[0153] Middle layer B (skeleton layer): 100 parts of ethylene-butene copolymer (ENGAGETM PV 8688), 1 part of crosslinking agent (TRIGONOX 42S), 0.5 parts of co-crosslinking agent (TAICROS), 0.5 parts of co-crosslinking agent (SR-351NS), 0.5 parts of tackifier (KBM-503)

[0154] The specific preparation process steps are as follows:

[0155] Step 1: Raw material mixing: Ethylene-octene copolymer (ENGAGE PV 8660), hindered amine light stabilizer (UV-770), ultraviolet absorber (UV-531), processing aid erucamide (Crodamide212), anti-acid additive aluminum oxide ( Mix the following ingredients in proportion: M632SP (Ethylene-Butene Copolymer (ENGAGE™ PV 8688), Crosslinker (TRIGONOX 42S), Co-crosslinker (TAICROS), Co-crosslinker (SR-351NS), and Tackifier (KBM-503) for the intermediate layer B (framework layer) in proportion and set aside. Mix the ingredients for the side layer A (micro-foam layer) at 25°C for 1 hour; mix the ingredients for the intermediate layer B (framework layer) at 38°C for 12 hours.

[0156] Step 2: Melt extrusion: The mixed formula of the middle layer B (skeleton layer) is extruded through a 180mm single-screw extruder with a screw length-diameter ratio of 35:1, an extrusion temperature of 75°C-85°C, and a screw speed of 35 rpm;

[0157] Step 3: Supercritical Fluid Microfoaming Extrusion: The mixed formulation of the side layer A (microfoaming layer) is melt-extruded through a 110mm co-rotating twin-screw extruder at an extrusion temperature of 85°C and a screw speed of 450rpm. Supercritical Fluid Microfoaming: During the extrusion process, supercritical fluid carbon dioxide is pumped in via a flowmeter as a foaming agent. By precisely controlling the pressure and temperature, the POE resin forms a uniform microporous structure with a porosity of approximately 15% and a pore size of approximately 25µm during the screw extrusion process. The amount of foaming agent added is 0.6% of the resin mass, the foaming temperature is 155°C, and the foaming pressure is 9MPa.

[0158] Step 4: The molten materials of the side layer A (micro-foam layer) and the middle layer B (skeleton layer) are respectively fed into the distributor through the channel. The distributor is a three-layer swing blade distributor, and the mold is a composite mold outside the film. The distributor and mold are each equipped with a mold temperature controller for independent temperature control. The temperature range of the distributor mold temperature controller is 80°C, and the temperature range of the mold mold temperature controller is 100°C. The ABA three-layer structure film is formed by three-layer co-extrusion technology. After casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding, a non-slip POE encapsulation film with anti-precipitation additives is obtained.

[0159] Comparative Example 1:

[0160] The difference between Comparative Example 1 and Example 1 is that the amount of foaming agent added to the edge layer A is 0% of the resin mass, the foaming temperature is 85° C., the foaming pressure is 0 MPa, and the extrusion temperature is 85° C. The remaining raw materials and process steps are the same as those in Example 1.

[0161] Comparative Example 2:

[0162] Comparative Example 1 differs from Example 1 in that the amount of foaming agent added to the edge layer A is 0% of the resin mass, the foaming temperature is 85°C, the foaming pressure is 0 MPa, and the extrusion temperature is 85°C. Only 100 parts of ethylene-octene copolymer (ENGAGE PV 8660) is added; no other additives are added. The remaining process steps are the same as in Example 1.

[0163] Comparative Example 3:

[0164] Comparative Example 1 differs from Example 1 in that the amount of foaming agent added to the edge layer A is 1.5%, the foaming temperature is 175°C, the foaming pressure is 15 MPa, and the extrusion temperature is 85°C. Only 100 parts of ethylene-octene copolymer (ENGAGE PV 8660) is added; no other additives are added. The remaining process steps are the same as in Example 1.

[0165] The porosity, pore size, friction coefficient, film tension, PCT adhesion, and DH attenuation of the POE encapsulation films prepared in the above examples and comparative examples are shown in Table 1.

[0166] in,

[0167] Porosity test reference: GB / T 1033.1-2016 "Plastics - Determination of density and relative density" calculated using high-precision instruments.

[0168] Pore ​​size test reference: ASTM B 827-2016 "Scanning Electron Microscopy Analysis Method" measures the size and distribution of pores in POE films.

[0169] The test method for the dynamic friction coefficient of the contact surface between POE film and glass refers to the standard: GB / T 10006-1988.

[0170] POE film and glass tensile test reference: T / CPIA 0006-2017.

[0171] The DH1000h of POE film refers to: IEC 61215 "Photovoltaic module performance test".

[0172] Table 1: POE encapsulation film performance test results

[0173]

[0174]

[0175] As can be seen from the results in Table 1, Examples 1-12 employ the method of the present invention to produce an anti-slip POE encapsulation film with anti-adjuvant precipitation, comprising an ABA three-layer functional layer design and a green preparation process using co-rotating twin-screw extruder supercritical fluid micro-foaming technology. The side layer A of the POE encapsulation film is a micro-foaming layer comprising a base resin and a micro-foaming POE resin loaded with an anti-aging agent, a processing aid, and an anti-acid agent. The POE resin has a porosity of 15%-30% and a pore size of 80nm-150nm. The middle layer B of the POE encapsulation film is a skeleton layer comprising a base resin, a cross-linking agent, a co-cross-linking agent, a tackifier, and the like.

[0176] Comparative Examples 1 and 2, where the side layer A was not micro-foamed, showed that POE micro-foaming effectively increased the initial kinetic friction coefficient (μs) between the POE film and the glass, as well as the kinetic friction coefficient (μs) between the film and the glass after 60 days of aging. The micro-foaming pores within the POE effectively physically adsorbed the migrating additive, effectively reducing its migration to the film surface and improving the film's surface roughness, thereby enhancing the POE film's anti-slip properties.

[0177] In comparative example 3, after the removal of the anti-aging agent, processing aid, and anti-acid additive loaded by the micro-foam layer, it was found that the adhesive film and glass PCT48h bonding force were significantly reduced after long-term placement for 60 days, and the DH1000h aging decay was significantly increased. By the pores of the internal micro-foaming of POE, the micro-particle size of the auxiliary agent can not only significantly increase its specific surface area in the matrix resin, but also can further optimize its dispersion and distribution in the matrix resin by the heterogeneous nucleation effect. These auxiliary agents are formed into a more stable dispersed phase in the POE matrix, thereby effectively improving the uniformity and stability of the auxiliary agent in the matrix resin, further promoting the wet-heat resistance of composite material. By this synergistic effect, not only the anti-auxiliary agent of the POE adhesive film can be improved to separate out the anti-skid ability, but also the comprehensive anti-aging performance of the POE adhesive film at the component end is improved.

[0178] In summary, the anti-slip POE encapsulation film with anti-additive precipitation and its preparation method adopt a supercritical fluid micro-foaming process to make the film have a uniform microporous structure. The physical foaming method can not only form effective physical adsorption of the surface additives, provide the surface roughness of the film while enhancing the anti-slip ability, but also further optimize the dispersion and distribution of each additive in the matrix resin through the heterogeneous nucleation effect. In addition, the optimized preparation process does not require the introduction of chemical additives for foaming, the production process is more environmentally friendly, and will not affect the performance of other inorganic additives.

[0179] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A method for preparing a POE encapsulation film, characterized in that: The steps include: S1, mixing raw materials: mixing the base resin, anti-aging agent, processing aid and anti-acid additive of the micro-foam layer and stirring evenly to obtain the raw material of the micro-foam layer; mixing the base resin, cross-linking agent, co-cross-linking agent and tackifier of the skeleton layer and stirring evenly to obtain the raw material of the skeleton layer; S2, melt extrusion, melt-extrude the skeleton layer raw material through a single-screw extruder, control the extrusion temperature and screw speed to obtain the skeleton layer; S3, supercritical fluid micro-foaming extrusion, melt-extrude the raw materials of the micro-foaming layer through a co-rotating twin-screw extruder, control the extrusion temperature and screw speed, and introduce supercritical fluid carbon dioxide as a foaming agent during the extrusion process, then heat and foam, the amount of the foaming agent added is 0.5% to 2% of the mass of the base resin, the foaming temperature is 160 to 200° C., and the foaming pressure is 10 to 20 MPa to obtain a micro-foaming layer; S4, cast film forming, the micro-foam layer, skeleton layer, and micro-foam layer are co-extruded into an ABA structural film through three layers, and then the POE encapsulation film is obtained through casting, embossing, cooling and shaping, thickness measurement, pulling, slitting, and winding.

2. The preparation method according to claim 1, wherein The matrix resin includes any one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, hyperbranched polyolefin elastomer, vinyl polyolefin elastomer, and ultra-low density polyethylene.

3. The preparation method according to claim 1, wherein The anti-aging agent includes any one or more combinations of antioxidants, light stabilizers, and ultraviolet absorbers; wherein The antioxidant includes any one or more combinations of hindered amine antioxidants, phosphite antioxidants, and thioester antioxidants; The light stabilizer is a hindered amine light stabilizer, including any one or a combination of two of dimethylpiperidine derivatives and disubstituted piperidine derivatives; The ultraviolet absorber includes any one or more combinations of benzotriazole light stabilizers, benzophenones, substituted acrylonitriles, triazines, salicylates, naphthotriazoles, phenols, and amides.

4. The preparation method according to claim 1, wherein The processing aid includes any one or more combinations of paraffin wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate wax, erucamide, and oleamide; The antacid auxiliary agent includes any one or more combinations of zinc oxide, aluminum oxide, magnesium oxide, calcium oxide, and potassium oxide.

5. The preparation method according to claim 1, wherein The cross-linking agent includes any one or more combinations of dicumyl peroxide, tert-butyl peroxide, tert-butyl acetyl peroxide, tert-butyl carbonate peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, and tert-butyl peroxy-3.5.5-trimethylhexanoate; The auxiliary cross-linking agent includes any one or more combinations of triallyl isocyanate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, and ditrimethylolpropane tetraacrylate; The adhesion promoter includes any one or more combinations of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.

6. The preparation method according to claim 1, wherein In step S1, the mixing and stirring temperature of the raw materials for the micro-foam layer is 25-35° C., and the stirring time is 1-2 hours. The mixing and stirring temperature of the raw materials for the skeleton layer is 38-42° C., and the stirring time is 1-15 hours.

7. The preparation method according to claim 1, wherein In step S2, the screw diameter of the single-screw extruder is any one of 150 mm, 160 mm, 180 mm, 200 mm, 220 mm, and 240 mm, the screw aspect ratio is any one of 20:1 to 40:1, the extrusion temperature is 70 to 110° C., and the screw speed is 30 to 50 rpm; The screw diameter of the co-rotating twin-screw extruder in step S3 is any one of 65 mm, 75 mm, 95 mm, 110 mm, and 135 mm, the screw aspect ratio is any one between 32:1 and 56:1, the extrusion temperature is 70-110° C., and the screw speed is 100-200 rpm.

8. A POE encapsulation film, characterized in that: include: The micro-foam layer, the skeleton layer and the micro-foam layer are sequentially stacked and co-extruded, with a thickness ratio ranging from 1:1:1 to 1:9:1; The porosity of the micro-foam layer is 15% to 30%, and the pore diameter is 5 μm to 80 μm.

9. The POE encapsulation film according to claim 8, wherein: The POE packaging film has a gram weight range of 50g / ㎡ to 500g / ㎡.

10. A photovoltaic module, characterized in that: It comprises the POE encapsulation film as described in any one of claims 8-9.

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