TW201912703A - Crosslinked weathering polyolefin film for solar battery backboard and preparation method thereof - Google Patents

Crosslinked weathering polyolefin film for solar battery backboard and preparation method thereof Download PDF

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TW201912703A
TW201912703A TW106130994A TW106130994A TW201912703A TW 201912703 A TW201912703 A TW 201912703A TW 106130994 A TW106130994 A TW 106130994A TW 106130994 A TW106130994 A TW 106130994A TW 201912703 A TW201912703 A TW 201912703A
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盛修業
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南亞塑膠工業股份有限公司
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Abstract

The prevent invention provides a cross-linked and weather-resistant polyolefin sheet for solar cell backplane and its preparation method. The cross-linked and weather-resistant polyolefin sheet is prepared by preliminarily mixing a polyolefin composition resin and a fluororesin in a mixer to form a mixture, wherein the fluororesin content is 0.2 to 5 parts by weight based on 100 parts by weight of the polyolefin composition resin. The mixture is uniformly kneaded with a kneader, and the composition of the mixture is subjected to gelation and crosslinking by a rolling mill. The gelled mixture is pelletized by a calender and the sheet is introduced into a cooling wheel set for cooling. The film produced by the present invention has good weatherability and stretchability, and is suitable for use in a back sheet of a solar cell.

Description

用於太陽電池背板的交聯耐候聚烯烴膠片及其製法    Cross-linked weather-resistant polyolefin film for solar cell back sheet and preparation method thereof   

本發明涉及一種用於太陽電池背板的交聯耐候聚烯烴膠片及其製法，特別是涉及一種含有氟樹脂的交聯耐候聚烯烴膠片及其製法。 The invention relates to a cross-linked weather-resistant polyolefin film for a solar cell back sheet and a method for manufacturing the same, and particularly to a cross-linked weather-resistant polyolefin film containing a fluorine resin and a method for manufacturing the same.

太陽能電池組件主要由玻璃蓋板、乙烯-醋酸乙烯共聚物(EVA)、電池片、背板、接線盒和邊框等組成。由於太陽能電池背板不僅對於電池片提供了支撐以及保護的作用，且是上述各元件中最直接與外界環境大面積接觸的封裝材料，其性能之優劣直接影響了太陽能電池組件的發電效率和使用壽命，因此，太陽能電池背板一般需要具備有可靠的絕緣性、阻水性、耐老化性、耐高低溫、耐腐蝕性，以使其能夠在戶外環境下防止水氣侵蝕，並且阻礙氧氣通過，進而能有效地保護太陽能電池的內部組件。此外，高效能的太陽能電池背板更需要具備能夠反射陽光的特性，以藉此提高太陽能電池組件整體的能量轉換效率。 The solar cell module is mainly composed of a glass cover plate, an ethylene-vinyl acetate copolymer (EVA), a battery sheet, a back plate, a junction box, and a frame. Since the solar cell backsheet not only provides support and protection for the cell sheet, but also is the packaging material that most directly contacts the external environment among the above components, its performance directly affects the power generation efficiency and use of the solar cell module. Life, therefore, the solar cell backsheet generally needs to have reliable insulation, water resistance, aging resistance, high and low temperature resistance, corrosion resistance, so that it can prevent water vapor erosion in the outdoor environment, and hinder the passage of oxygen, Furthermore, the internal components of the solar cell can be effectively protected. In addition, high-efficiency solar cell backsheets also need to be capable of reflecting sunlight, thereby improving the overall energy conversion efficiency of the solar cell module.

太陽電池背板主要分為含氟背板與不含氟背板兩大類。其中含氟背板又分雙面含氟(如TPT)與單面含氟(如TPE)兩種；而不含氟的背板則多通過膠粘劑將多層PET膠粘複合而成。目前，商用晶矽太陽電池組件的使用要求為25年，因此，如果背板在耐老化、耐絕緣、耐水氣等方面無法滿足太陽電池組件25年的 環境考驗，最終將導致太陽電池的可靠性、穩定性與耐久性無法得到保障，而可能逐漸出現脫層、龜裂、起泡及/或黃變等不良現象，進而導致電池模塊脫落、電池片滑移、電池有效輸出功率降低等結果。更有甚者，甚至可能造成電池組件會在較低電壓和電流值的情況下出現電打弧現象，而引起電池組件燃燒並促發火災，造成人員安全損害和財產損失。 Solar battery backplanes are mainly divided into two categories: fluorine-containing backplanes and fluorine-free backplanes. The fluorine-containing backsheet is divided into two kinds of fluorine-containing (such as TPT) and single-sided fluorine (such as TPE); the fluorine-free backsheet is usually made by laminating multiple layers of PET with an adhesive. At present, the use of commercial crystalline silicon solar cell modules requires 25 years. Therefore, if the backplane cannot meet the 25-year environmental test of solar cell modules in terms of aging resistance, insulation resistance, and moisture resistance, it will eventually lead to the reliability of solar cells. , Stability and durability cannot be guaranteed, and delamination, cracking, blistering, and / or yellowing may gradually occur, which may lead to battery module shedding, battery slippage, and reduced effective output power of the battery. What's more, it may even cause the arcing phenomenon of the battery pack at a lower voltage and current value, which will cause the battery pack to burn and cause a fire, resulting in personal safety damage and property damage.

太陽能背板用之氟膜，現有的製造方式，主要是將氟樹脂(如PVF、PVDF、PTFE及ECTFE等)透過吹膜(Blow)、T-die加工或塗布型加工等方式加工而成。其中，吹膜是將氟樹脂粒子添加一些助劑後，熔融擠出成型管狀膜坯，在較好的熔體流動狀態下通過高壓空氣將管膜吹脹到所要求的厚度，經冷卻定型後成為薄膜；T-die加工方式則是將氟樹脂與其它材質(如PMMA或PET等)在熔融態下，透過多層共擠出的方式而得的多層膜；塗布型加工則是將氟樹脂藉由溶劑溶解後，塗布於PET等基材表面，並經由乾燥而得最終產品。 The current manufacturing method of the fluorine film for solar back sheet is mainly made by processing fluorine resin (such as PVF, PVDF, PTFE, ECTFE, etc.) through blown film, T-die processing, or coating type processing. Among them, the blown film is made by adding fluororesin particles to some additives, and then melt-extruding the tubular film blank. In a good melt flow state, the tube film is blown to the required thickness by high-pressure air. After cooling and shaping It becomes a film; T-die processing method is a multilayer film obtained by multi-layer coextrusion of fluororesin and other materials (such as PMMA or PET) in a molten state; coating type processing uses fluororesin to borrow After being dissolved in a solvent, it is coated on the surface of a substrate such as PET and dried to obtain a final product.

氟樹脂因其本身的熔點高，常因分散均勻性不佳，造成加工效率不高，因此導致整個產品的售價居高不下。而將氟樹脂與其它樹脂做內部添加時，亦需要控制比例，並克服其與PP等聚烯烴樹脂的相容分散性的問題。 Because of its high melting point, fluororesin often has poor processing uniformity, resulting in low processing efficiency, which leads to the high price of the entire product. When fluorine resin and other resins are added internally, it is also necessary to control the ratio and overcome the problem of compatibility and dispersibility with polyolefin resins such as PP.

本發明所要解決的技術問題在於，針對現有技術的不足提供一種交聯耐候聚烯烴膠片及其製法，特別是相較於現有技術中，直接以純氟樹脂製成的膠片作為太陽電池背板的技術方案，能夠以較低的成本達到同樣優異的耐候特性，且具備更佳的抗拉伸特性的一種含有氟樹脂的交聯耐候聚烯烴膠片及其製法。 The technical problem to be solved by the present invention is to provide a cross-linked weather-resistant polyolefin film and a method for making the same in view of the shortcomings of the prior art, especially compared with the prior art, a technology of directly using a film made of pure fluororesin as a solar cell back sheet. Solution, a fluororesin-containing cross-linked weather-resistant polyolefin film capable of achieving the same excellent weather-resistance characteristics at a lower cost and having better tensile properties, and a method for producing the same.

為了解決上述的技術問題，本發明所採用的其中一技術方案是，提供一種交聯耐候聚烯烴膠片，其包含聚烯烴組合物樹脂以及氟樹脂，其特徵在於，所述氟樹脂的含量相對於100重量份(parts per hundreds of rubber/resin，簡稱PHR)的所述聚烯烴組合物樹脂為0.2~5 PHR，所述氟樹脂選自聚偏二氟乙烯(Polyvinylidene difluoride，簡稱PVDF)、聚四氟乙烯(Polytetrafluoroethylene，簡稱PTFE)、乙烯-四氟乙烯共聚物(Ethylene tetrafluoroethylene，簡稱ETFE)、聚三氟氯乙烯(Polychlorotrifluoroethene，簡稱PCTFE)以及乙烯-聚三氟氯乙烯共聚物(Ethylene Polychlorotrifluoroethene，簡稱ECTFE)之中的一種或兩種以上的組合。 In order to solve the above technical problem, one of the technical solutions adopted by the present invention is to provide a cross-linked weather-resistant polyolefin film, which comprises a polyolefin composition resin and a fluororesin, and is characterized in that the content of the fluororesin relative to 100 parts by weight (parts per hundreds of rubber / resin, referred to as PHR) of the polyolefin composition resin is 0.2 to 5 PHR, and the fluororesin is selected from Polyvinylidene difluoride (PVDF), polytetrafluoroethylene Polytetrafluoroethylene (PTFE), Ethylene tetrafluoroethylene (ETFE), Polychlorotrifluoroethene (PCTFE), and Ethylene Polychlorotrifluoroethene (PCTFE) ECTFE).

優選地，所述交聯耐候聚烯烴膠片，還包含交聯劑、交聯助劑、滑劑、助劑、抗氧化劑、以及色料，其中，所述交聯劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~5 PHR，所述交聯劑為有機過氧化物交聯劑；所述交聯助劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0~2 PHR，其選自二終端碳-碳雙鍵之二烯烴、二終端碳-碳雙鍵之三烯烴、二終端碳-碳雙鍵之四烯烴(An alkadiene,alkatriene,or alkatetraene compound comprising at least two terminal carbon-carbon double bonds)、三烯丙基異三聚氰酸酯(Triallyl isocyanurate，簡稱TAIC)、三羥甲基丙烷三丙烯酸酯(Trimethylolpropane Triacrylate，簡稱TMPTA)以及奈米級二氧化鈦(TiO2)之中的一種或兩種以上的組合；所述滑劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~15 PHR；所述助劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~80 PHR；所述抗氧化劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~5 PHR，其選自酚類抗氧劑或亞磷酸三苯酯類抗氧劑；所述色料的含量相對於100 PHR的所述聚烯烴組合物樹脂為0~35 PHR。 Preferably, the cross-linked weather-resistant polyolefin film further comprises a cross-linking agent, a cross-linking assistant, a slip agent, an auxiliary agent, an antioxidant, and a colorant, wherein the content of the cross-linking agent is relative to 100 PHR. The polyolefin composition resin is 0.1 to 5 PHR, and the cross-linking agent is an organic peroxide cross-linking agent; the content of the cross-linking assistant is 0 to 100 PHR of the polyolefin composition resin. 2 PHR, which is selected from the group consisting of two-terminal carbon-carbon double bond diolefins, two-terminal carbon-carbon double bond triolefins, and two-terminal carbon-carbon double bond tetraolefins two terminal carbon-carbon double bonds), Triallyl isocyanurate (TAIC), Trimethylolpropane Triacrylate (TMPTA), and nano-sized titanium dioxide (TiO 2 1) or a combination of two or more of them; the content of the lubricant is 0.1 to 15 PHR relative to the polyolefin composition resin of 100 PHR; the content of the auxiliary agent is relative to the polymer of 100 PHR The olefin composition resin is 0.1 to 80 PHR; said The content of the oxidizing agent relative to the polyolefin composition resin of 100 PHR is 0.1 to 5 PHR, which is selected from the group consisting of phenolic antioxidants or triphenyl phosphite antioxidants; the content of the colorant is relative to 100 PHR The polyolefin composition resin is 0 to 35 PHR.

優選地，所述助劑為紫外線吸收劑以及填充劑之中的一種或混合並用。其中，所述填充劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~30 PHR；所述紫外線吸收劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~3 PHR，其選自受阻胺類光安定劑、羥基苯基苯并三唑類紫外線吸收劑或羥基二苯甲酮類紫外線吸收劑之中的一種或兩種以上的組合。 Preferably, the auxiliary agent is one of a UV absorber and a filler, or is used in combination. Wherein, the content of the filler is 0.1 to 30 PHR relative to the polyolefin composition resin of 100 PHR; the content of the ultraviolet absorber is 0.1 to 3 PHR relative to the polyolefin composition resin of 100 PHR. It is selected from one or a combination of two or more of a hindered amine light stabilizer, a hydroxyphenylbenzotriazole ultraviolet absorber, or a hydroxybenzophenone ultraviolet absorber.

優選地，所述聚烯烴組合物樹脂選自聚乙烯(Polyethylene，簡稱PE)、聚丙烯(Polypropylene，簡稱PP)以及乙烯-醋酸乙烯酯共聚合物(Ethylene-vinyl acetate Copolymer，簡稱EVA)之中的兩種或兩種以上的組合。 Preferably, the polyolefin composition resin is selected from the group consisting of polyethylene (PE), polypropylene (PP), and ethylene-vinyl acetate copolymer (EVA). A combination of two or more.

優選地，所述聚乙烯的含量為20至50 PHR，所述聚乙烯為乙烯均聚物，或乙烯和具有3至12個碳原子的α-烯烴的共聚物；所述聚丙烯的含量為30至60 PHR，所述聚丙烯為丙烯均聚物與丙烯和一種或多種其它α-烯烴的共聚物，其中丙烯的聚合物部分至少占共聚物重量的60%；所述乙烯-醋酸乙烯酯共聚合物的含量為0.1至30 PHR，所述乙烯-醋酸乙烯酯共聚合物中醋酸乙烯酯的含量(Vinyl Acetate content，簡稱VA content)佔乙烯-醋酸乙烯酯共聚合物總量的8~33%。 Preferably, the content of the polyethylene is 20 to 50 PHR, the polyethylene is an ethylene homopolymer, or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms; the content of the polypropylene is 30 to 60 PHR, the polypropylene is a copolymer of a propylene homopolymer with propylene and one or more other alpha-olefins, wherein the polymer portion of propylene accounts for at least 60% of the weight of the copolymer; the ethylene-vinyl acetate The content of the copolymer is 0.1 to 30 PHR, and the content of vinyl acetate (Vinyl Acetate content, VA content for short) in the ethylene-vinyl acetate copolymer is 8 to 8% of the total ethylene-vinyl acetate copolymer. 33%.

優選地，所述氟樹脂為分子量介於25萬至100萬的聚四氟乙烯。 Preferably, the fluororesin is polytetrafluoroethylene with a molecular weight between 250,000 and 1 million.

優選地，所述交聯耐候聚烯烴膠片對波長介於420至650nm的光線反射率大於65%。 Preferably, the cross-linked weather-resistant polyolefin film has a reflectance of light with a wavelength between 420 and 650 nm of more than 65%.

為了解決上述的技術問題，本發明所採用的另外一技術方案是，提供一種交聯耐候聚烯烴膠片的製法，其包括下列步驟：將聚烯烴組合物樹脂以及氟樹脂以混合機進行預攪拌以形成一混合物，其中，所述氟樹脂含量相對於100 PHR的所述聚烯烴組合物樹脂為0.2~5 PHR；以一捏合機對所述混合物進行均勻混煉；以一軋輪機使所述混合物的成分進行膠化及交聯；將膠化後的所述混合物以一壓延機製成一片體；以及將所述片體引入冷卻輪組冷卻定型。 In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a method for manufacturing a cross-linked weather-resistant polyolefin film, which includes the following steps: pre-stirring the polyolefin composition resin and fluororesin with a mixer to A mixture is formed, wherein the fluororesin content is 0.2 to 5 PHR relative to the polyolefin composition resin of 100 PHR; the mixture is uniformly kneaded by a kneader; the mixture is made by a rolling mill Gelatinize and cross-link the ingredients; make the gelatinized mixture into a sheet by a calender; and introduce the sheet into a cooling wheel set to cool and shape.

優選地，在進行預攪拌以形成所述混合物的步驟中，還混合 有交聯劑、交聯助劑、滑劑、助劑以及色料。其中，交聯劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~5 PHR，所述交聯劑為有機過氧化物交聯劑；交聯助劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0~2 PHR，其選自二終端碳-碳雙鍵之二烯烴、三烯烴化合物、四烯烴化合物、TAIC、三羥甲基丙烷三丙烯酸酯以及奈米級二氧化鈦之中的一種或兩種以上的組合；滑劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~15 PHR；助劑的含量相對於100 PHR的所述聚烯烴組合物樹脂為0.1~80 PHR；色料的含量相對於100 PHR的所述聚烯烴組合物樹脂為0~35 PHR。 Preferably, in the step of performing pre-stirring to form the mixture, a cross-linking agent, a cross-linking auxiliary agent, a slip agent, an auxiliary agent, and a colorant are further mixed. Wherein, the content of the crosslinking agent is 0.1 to 5 PHR relative to the polyolefin composition resin of 100 PHR, and the crosslinking agent is an organic peroxide crosslinking agent; the content of the crosslinking assistant is relative to 100 PHR. The polyolefin composition resin is 0 to 2 PHR, which is selected from the group consisting of diolefins, triolefin compounds, tetraolefin compounds, TAIC, trimethylolpropane triacrylate, and nano-grade titanium dioxide, which have two terminal carbon-carbon double bonds. One or a combination of two or more of them; the content of the lubricant relative to the polyolefin composition resin of 100 PHR is 0.1 to 15 PHR; the content of the additive relative to the polyolefin composition resin of 100 PHR is 0.1 to 80 PHR; the content of the colorant is 0 to 35 PHR relative to the polyolefin composition resin of 100 PHR.

優選地，所述軋輪機以及所述壓延機作業的溫度控制在130至220℃之間。 Preferably, the operating temperature of the rolling mill and the calender is controlled between 130 and 220 ° C.

優選地，所述氟樹脂為平均粒徑介於3至10μm的粉末，且所述氟樹脂為分子量介於25萬至100萬的聚四氟乙烯。 Preferably, the fluororesin is a powder having an average particle diameter of 3 to 10 μm, and the fluororesin is polytetrafluoroethylene having a molecular weight of 250,000 to 1 million.

本發明的其中一有益效果在於，本發明所提供的交聯耐候聚烯烴膠片及其製法，其能通過“添加相對於100 PHR的聚烯烴組合物樹脂含量為0.2~5 PHR的氟樹脂”的技術方案，使得所製成的交聯耐候聚烯烴膠片具備良好的耐候特性，相較於現有技術中，直接以純氟樹脂製成的膠片作為太陽電池背板的技術方案，本發明不但能夠以較低的成本達到同樣優異的耐候特性，此外，更具備相較於現有技術更佳的拉伸性。 One of the beneficial effects of the present invention is that the cross-linked weather-resistant polyolefin film provided by the present invention and the method for preparing the same can pass the "addition of a fluororesin with a resin content of 0.2 to 5 PHR relative to the polyolefin composition of 100 PHR". The technical solution makes the manufactured cross-linked weather-resistant polyolefin film have good weather resistance characteristics. Compared with the prior art, a film made of pure fluororesin is directly used as a technical solution for a solar cell back sheet. It also achieves the same excellent weather resistance at a low cost, and in addition, it has better stretchability compared to the prior art.

為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有關本發明的詳細說明與附圖，然而所提供的附圖僅用於提供參考與說明，並非用來對本發明加以限制。 In order to further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description, and are not intended to limit the present invention.

圖1為本發明實施例的交聯耐候聚烯烴膠片的製法流程示意圖。 FIG. 1 is a schematic flowchart of a method for manufacturing a cross-linked weatherable polyolefin film according to an embodiment of the present invention.

以下是通過特定的具體實施例來說明本發明所公開有關“交 聯耐候聚烯烴膠片及其製法”的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用，本說明書中的各項細節也可基於不同觀點與應用，在不悖離本發明的精神下進行各種修飾與變更。另外，本發明的附圖僅為簡單示意說明，並非依實際尺寸的描繪，事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。 The following are specific embodiments to explain the embodiments of the present invention related to "crosslinked weather-resistant polyolefin film and its manufacturing method". Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention may be implemented or applied through other different specific embodiments, and various details in this specification may also be based on different viewpoints and applications, and various modifications and changes may be made without departing from the spirit of the present invention. In addition, the drawings of the present invention are merely a schematic illustration, and are not drawn according to actual dimensions, and are stated in advance. The following embodiments will further describe the related technical content of the present invention in detail, but the disclosed content is not intended to limit the protection scope of the present invention.

請參閱圖1所示，圖1為本發明實施例的交聯耐候聚烯烴膠片的製法流程示意圖。本發明的交聯耐候聚烯烴膠片的製法，其特徵是添加相對於100 PHR的聚烯烴組合物樹脂含量為0.2~5 PHR的氟樹脂，並經由分散處理，使得氟樹脂能夠充分且均勻地分散於聚烯烴組合物樹脂中，而且於加工成型過程均勻交聯，強化膠片的耐候性以及拉伸性。其具體流程，包括下列各個主要步驟：S100：將聚烯烴組合物樹脂以及氟樹脂以混合機進行預攪拌以形成一混合物，其中，氟樹脂含量相對於100 PHR的聚烯烴組合物樹脂為0.2~5 PHR；S102：以一捏合機對混合物進行均勻混煉；S104：以一軋輪機使混合物的成分進行膠化及交聯；S106：將膠化後的混合物以一壓延機製成一片體；以及S108：將片體引入冷卻輪組冷卻定型。 Please refer to FIG. 1, which is a schematic flowchart of a method for manufacturing a cross-linked weatherable polyolefin film according to an embodiment of the present invention. The method for producing a crosslinked weather-resistant polyolefin film of the present invention is characterized by adding a fluororesin having a resin content of 0.2 to 5 PHR relative to 100 PHR of the polyolefin composition and subjecting it to a dispersion treatment so that the fluororesin can be sufficiently and uniformly dispersed. In the polyolefin composition resin, it is evenly cross-linked during processing and molding to strengthen the weather resistance and stretchability of the film. The specific process includes the following main steps: S100: The polyolefin composition resin and the fluororesin are pre-mixed by a mixer to form a mixture, wherein the content of the fluororesin relative to the polyolefin composition resin of 100 PHR is 0.2 ~ 5 PHR; S102: uniformly knead the mixture with a kneader; S104: gelate and crosslink the components of the mixture with a rolling mill; S106: make the gelled mixture into a single body with a calender; And S108: the sheet body is introduced into the cooling wheel set for cooling and setting.

更具體地說，本發明的交聯耐候聚烯烴膠片的製法，首先利用混合機使適當比例的聚烯烴組合物樹脂以及氟樹脂在低溫條件下進行預混合(步驟S100)。其中，所使用的聚烯烴組合物樹脂，可為交聯熱塑性樹脂。樹脂可以是均聚物或者為兩種或多種共聚用單體產生的共聚物，以及一種或多種聚合物的摻合物。生產這 些均聚物和共聚物所用的單體可具有2至20個碳原子，較佳可採用具有2至12個碳原子的單體。聚烯烴組合物樹脂選自非聚氯乙烯之塑料，可採用聚乙烯、聚丙烯、乙烯-醋酸乙烯酯共聚合物、熱塑性聚烯烴(Thermoplastic polyolefin，簡稱TPO)或熱塑性塑膠彈性體(Thermoplastic Elastomer，簡稱TPE)之中的兩種或兩種以上的組合。 More specifically, in the method for producing a cross-linked weather-resistant polyolefin film of the present invention, first, the polyolefin composition resin and the fluororesin in an appropriate ratio are pre-mixed at a low temperature using a mixer (step S100). Among them, the polyolefin composition resin used may be a crosslinked thermoplastic resin. The resin may be a homopolymer or a copolymer produced from two or more comonomers, and a blend of one or more polymers. The monomers used to produce these homopolymers and copolymers may have 2 to 20 carbon atoms, and monomers having 2 to 12 carbon atoms are preferably used. The polyolefin composition resin is selected from plastics other than polyvinyl chloride. Polyethylene, polypropylene, ethylene-vinyl acetate copolymers, thermoplastic polyolefins (TPO) or thermoplastic plastic elastomers (Thermoplastic Elastomer, TPE) for two or more combinations.

其中，聚乙烯的含量為20至50 PHR，聚乙烯為乙烯均聚物，或乙烯和具有3至12個碳原子(較佳為4至8個碳原子，並可以視實際需求選用二烯)的α-烯烴的共聚物，或其混合物以及此類均聚物和共聚物的摻合物，混合物可機械混合或現場混合。α-烯烴可選自丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯及1-辛烯。聚乙烯還可以為乙烯和一種不飽和酯的共聚物，如乙烯酯(乙酸乙烯酯)或丙烯酸酯以及甲基丙烯酸酯。聚乙烯可以為均相或多相，均相聚乙烯一般具有大約1.5至大約3.5的多分散度(重量平均分子量/數平均分子量，即Mw/Mn)，且具有基本均勻的共聚用單體分布。此外，多相聚乙烯具有大於3.5的多分散度而且具有不均勻的共聚單體分布。具體來說，本發明的聚乙烯可以是高密度聚乙烯(High Density Polyethylene，簡稱HDPE)、低密度聚乙烯(Low Density Plyethylene，簡稱LDPE)、線性低密度聚乙烯(Low Linear Density Polyethylene，簡稱LLDPE)或是茂金屬PE(Metallocene Polyethylene，簡稱mPE)。 Among them, the content of polyethylene is 20 to 50 PHR, polyethylene is an ethylene homopolymer, or ethylene and has 3 to 12 carbon atoms (preferably 4 to 8 carbon atoms, and diene can be selected according to actual needs) Copolymers of alpha-olefins, or mixtures thereof, and blends of such homopolymers and copolymers, the mixtures may be mechanically or in-situ. The alpha-olefin may be selected from propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Polyethylene can also be a copolymer of ethylene and an unsaturated ester, such as vinyl ester (vinyl acetate) or acrylate and methacrylate. The polyethylene may be homogeneous or heterogeneous. The homogeneous polyethylene generally has a polydispersity (weight average molecular weight / number average molecular weight, ie, Mw / Mn) of about 1.5 to about 3.5, and has a substantially uniform comonomer distribution. In addition, heterophasic polyethylene has a polydispersity greater than 3.5 and has an uneven comonomer distribution. Specifically, the polyethylene of the present invention may be High Density Polyethylene (HDPE), Low Density Plyethylene (LDPE), Low Linear Density Polyethylene (LLDPE) ) Or metallocene PE (Metallocene Polyethylene, mPE for short).

聚丙烯的含量為30至60 PHR，聚丙烯為丙烯均聚物與丙烯和一種或多種其它α-烯烴的共聚物，其中丙烯的聚合物部分至少占共聚物重量的60%。具體來說，可以是均聚聚丙烯(polypropylene homopolymer，簡稱PP-H)、嵌段共聚聚丙烯(polypropylene block copolymer，簡稱PP-B)、無規共聚聚丙烯(polypropylene random copolymer，簡稱PP-B)。 The content of polypropylene is 30 to 60 PHR. Polypropylene is a copolymer of a propylene homopolymer with propylene and one or more other α-olefins, wherein the polymer portion of propylene accounts for at least 60% by weight of the copolymer. Specifically, it may be a polypropylene homopolymer (PP-H), a block copolymer polypropylene (PP-B), or a random copolymer polypropylene (PP-B) ).

乙烯-醋酸乙烯酯共聚合物的含量為0.1至30 PHR。值得特別 一提的是，為了使太陽能電池背板的封裝作業良好，因此要求所使用的膠片與EVA之間具有強力的接著強度，但要避免產生黏輪情形而能夠適合於機具的成形加工，因此，在本發明的較佳實施例中，所導入的乙烯-醋酸乙烯酯共聚合物，其VA content為8~33%，偏高或偏低將導致不適合用於機具加工，或導致接著強度不足，最佳的VA content為18~33%。 The ethylene-vinyl acetate copolymer has a content of 0.1 to 30 PHR. It is worth mentioning in particular that in order to make the solar cell backsheet package work well, it is required to have a strong bonding strength between the used film and EVA, but to avoid the situation of sticking wheels, it can be suitable for the forming process of the equipment, Therefore, in the preferred embodiment of the present invention, the VA content of the introduced ethylene-vinyl acetate copolymer is 8 to 33%. A high or low VA content will result in unsuitability for machine tool processing or adhesion strength. Insufficient, the best VA content is 18 ~ 33%.

此外，本發明所添加的氟樹脂是選自PVDF、PTFE、ETFE、PCTFE以及ECTFE之中的一種或兩種以上的組合。通過添加適當比例的的氟樹脂(相對於100 PHR的聚烯烴組合物樹脂含量為0.2~5 PHR的氟樹脂)，使得所製成的交聯耐候聚烯烴膠片具備良好的耐候特性，且藉由聚烯烴組合物樹脂與氟樹脂的適當混合，也能產生較一般氟樹脂更佳的拉伸特性。 In addition, the fluororesin added in the present invention is one or a combination of two or more kinds selected from PVDF, PTFE, ETFE, PCTFE, and ECTFE. By adding an appropriate proportion of fluororesin (a fluororesin with a resin content of 0.2 to 5 PHR relative to a polyolefin composition of 100 PHR), the resulting cross-linked weather-resistant polyolefin film has good weather resistance characteristics. Proper blending of the polyolefin composition resin with the fluororesin can also produce better tensile properties than ordinary fluororesins.

另外，為了使氟樹脂能夠充分均勻地分散在聚烯烴組合物樹脂中，以避免產品因為各成分分散不均而產生麻面等現象，本發明較佳實施例中所採用的氟樹脂，為平均粒徑介於3至10μm的粉末，更佳為平均粒徑介於4.5至8μm的粉末。此外，在本發明的較佳實施例中，氟樹脂為分子量介於25萬至100萬的聚四氟乙烯。 In addition, in order to enable the fluororesin to be sufficiently uniformly dispersed in the polyolefin composition resin, to avoid the phenomenon of matting due to uneven dispersion of various components, the fluororesin used in the preferred embodiment of the present invention is an average A powder having a particle diameter of 3 to 10 μm, more preferably a powder having an average particle diameter of 4.5 to 8 μm. In addition, in a preferred embodiment of the present invention, the fluororesin is polytetrafluoroethylene having a molecular weight between 250,000 and 1 million.

為了在後續製程中，使聚烯烴組合物樹脂與氟樹脂能夠充分交聯以及膠化，並且便利後續加工程序之進行，在本發明的較佳實施例中，還可以在預混合的步驟就先添加交聯劑、交聯助劑、滑劑、助劑、抗氧化劑以及色料等添加劑。其中，交聯劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~5 PHR；交聯助劑的含量相對於100 PHR的聚烯烴組合物樹脂為0~2 PHR；滑劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~15 PHR；助劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~80 PHR；抗氧化劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~5 PHR，其選自酚類抗氧劑或亞磷酸三苯酯類抗氧劑；色料的含量相對於100 PHR的聚烯烴組合物樹脂為0~35 PHR。 In order to enable the polyolefin composition resin and the fluororesin to be fully cross-linked and gelled in the subsequent process, and to facilitate the subsequent processing procedures, in the preferred embodiment of the present invention, the pre-mixing step may be performed first. Add additives such as cross-linking agents, cross-linking aids, lubricants, auxiliaries, antioxidants, and colorants. Among them, the content of the crosslinking agent is 0.1 to 5 PHR relative to the polyolefin composition resin of 100 PHR; the content of the crosslinking assistant is 0 to 2 PHR relative to the polyolefin composition resin of 100 PHR; the content of the lubricant is relatively The polyolefin composition resin at 100 PHR is 0.1 to 15 PHR; the content of additives is 0.1 to 80 PHR relative to the polyolefin composition resin at 100 PHR; the antioxidant content is relative to the polyolefin composition resin at 100 PHR. 0.1 ~ 5 PHR, which is selected from phenolic antioxidants or triphenylphosphite antioxidants; the content of colorant is 0 ~ 35 PHR relative to the polyolefin composition resin of 100 PHR.

本發明所採用的交聯劑是有機過氧化物交聯劑，當溫度升高到過氧化物的分解溫度時便開始分解，並與聚烯烴樹脂發生反應而交聯成網狀結構。有機過氧化物在110至220℃之分解溫度範圍內，其半衰期為10分鐘。具體而言，可採用下列化合物：過氧化丁二酸(110℃)、過氧化苯甲醯(110℃)、2-乙基己酸過氧第三丁酯(113℃)、過氧化對氯苯甲醯(115℃)、過氧化異丁酸第三丁酯(115℃)、過氧化異丙基碳酸第三丁酯(135℃)、過氧化月桂酸第三丁酯(140℃)、2,5-二甲基-2,5-二(過氧苯甲醯基)己烷(140℃)、過氧乙酸第三丁酯(140℃)、過氧化鄰苯二甲酸二-第三丁酯(140℃)、過氧順丁烯二酸-第三丁酯(140℃)、過氧環己酮(145℃)、過氧苯甲酸-第三丁酯(145℃)、過氧化二枯基(150℃)、2,5-二甲基-2,5-二(第三-丁基-過氧化)己烷(155℃)、過氧第三-丁基枯(155℃)、第三-丁基過氧化氫(158℃)、二-第三丁基過氧化物(160℃)、2,5-二甲基-2,5-二(第三-丁基過氧化)己炔(170℃)以及α,α’-雙-第三-丁基過氧化-1,4-二異丙基苯(160℃)。以選擇α,α’-雙-第三-丁基過氧化-1,4-二異丙基苯及2,5-二甲基-2,5-二(第三-丁基過氧化)己炔。上列括號內所標示的溫度是各別化合物半衰期為10分鐘時對應的分解溫度。為了避免在加工的前段製程中(混合機或捏合機作業的過程中)就先發生交聯反應，而影響產品均勻性以及品質，或增加後段加工製成的困難度，可以採用分解溫度較高的有機過氧化物交聯劑，以確保前段製程能控制在分解溫度以下，進而提高批內物性及外觀品質穩定性。 The crosslinking agent used in the present invention is an organic peroxide crosslinking agent. When the temperature rises to the decomposition temperature of the peroxide, it starts to decompose, and reacts with the polyolefin resin to crosslink into a network structure. Organic peroxides have a half-life of 10 minutes in the decomposition temperature range of 110 to 220 ° C. Specifically, the following compounds can be used: succinic acid peroxide (110 ° C), benzoic acid peroxide (110 ° C), tert-butyl peroxy-2-ethylhexanoate (113 ° C), p-chloroperoxide Benzamidine (115 ° C), third butyl peroxyisobutyrate (115 ° C), third butyl peroxide isopropyl carbonate (135 ° C), third butyl peroxide laurate (140 ° C), 2,5-dimethyl-2,5-bis (peroxybenzylidene) hexane (140 ° C), tertiary butyl peroxyacetate (140 ° C), peroxodiphthalic acid di-third Butyl ester (140 ° C), maleic acid-third butyl ester (140 ° C), cyclohexanone peroxide (145 ° C), peroxybenzoic acid-third butyl ester (145 ° C), peroxidation Dicumyl (150 ° C), 2,5-dimethyl-2,5-bis (third-butyl-peroxy) hexane (155 ° C), peroxy tertiary-butylcumin (155 ° C) Tertiary-butyl hydroperoxide (158 ° C), di-tertiary butyl peroxide (160 ° C), 2,5-dimethyl-2,5-di (tertiary-butyl peroxide) Hexyne (170 ° C) and α, α'-bis-tertiary-butylperoxy-1,4-diisopropylbenzene (160 ° C). To select α, α'-bis-tertiary-butylperoxy-1,4-diisopropylbenzene and 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane Alkyne. The temperatures indicated in parentheses above are the decomposition temperatures corresponding to the half-lives of the individual compounds at 10 minutes. In order to avoid the cross-linking reaction in the first stage of the process (during the operation of the mixer or kneader), which affects the uniformity and quality of the product, or increases the difficulty of the later stage processing, a higher decomposition temperature can be used Organic peroxide cross-linking agent to ensure that the previous process can be controlled below the decomposition temperature, thereby improving the batch physical properties and appearance quality stability.

交聯助劑選自二終端碳-碳雙鍵之二烯烴、二終端碳-碳雙鍵之三烯烴、二終端碳-碳雙鍵之四烯烴(An alkadiene,alkatriene,or alkatetraene compound comprising at least two terminal carbon-carbon double bonds)、TAIC交聯助劑、TMPTA交聯助劑以及奈米級TiO2之中的一種或兩種以上的組合。更具體而言，可 採用1,9-癸二烯(1,9-decadiene)、1,7-辛二烯(1,7-octadiene)、1,5-己二烯(1,5-hexadiene)、1,4-戊二烯(1,4-pentadiene)、1,3-丁二烯(1,3-butadiene)、1,3,5-己三烯(1,3,5-hexatriene)、2,3-二甲基-1,3-丁二烯(2,3-dimethyl-1,3-butadiene)等一種以上的交聯助劑。此外，奈米級TiO2也可以作為另一種交聯助劑，其作用在於能夠促使樹脂與交聯劑在150℃~220℃的作業溫度下，於軋輪機中適當地進行交聯反應，而不必再另外藉助幅射線照射以提高交聯度。藉由添加奈米級TiO2可以使所生成之聚烯烴膜外觀及物性均勻，與上述二烯烴等交聯助劑併用，更可發揮優異的交聯效果。 Crosslinking auxiliaries are selected from two-terminal carbon-carbon double bond diolefins, two-terminal carbon-carbon double bond triolefins, and two-terminal carbon-carbon double bond tetraolefins (An alkadiene, alkatriene, or alkatetraene compound comprising at least two terminal carbon-carbon double bonds), TAIC cross-linking assistant, TMPTA cross-linking assistant, and nano-grade TiO 2 or a combination of two or more. More specifically, 1,9-decadiene, 1,7-octadiene, 1,5-hexadiene (1,5-hexadiene) can be used. ), 1,4-pentadiene (1,4-pentadiene), 1,3-butadiene (1,3-butadiene), 1,3,5-hexatriene (1,3,5-hexatriene) , 2,3-dimethyl-1,3-butadiene (2,3-dimethyl-1,3-butadiene) and more than one crosslinking assistant. In addition, nano-sized TiO 2 can also be used as another crosslinking assistant, which can promote the crosslinking reaction between the resin and the crosslinking agent in a rolling mill at an operating temperature of 150 ° C to 220 ° C, and It is no longer necessary to use additional radiation to increase the degree of crosslinking. The addition of nano-sized TiO 2 can make the appearance and physical properties of the resulting polyolefin film uniform, and it can be used in combination with the above-mentioned cross-linking assistants such as diolefins to further exhibit excellent cross-linking effects.

助劑為紫外線吸收劑以及填充劑之中的一種或混合並用。其中，紫外線吸收劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~3 PHR，其作用是為了消滅紫外光照射過程中產生的自由基，從而防止鏈的增長，降低光降解或光氧化的發生。一般為受阻胺類化合物，受阻胺在有氧狀態下吸收光能後，可以轉變為相應的氮氧自由基，進而捕獲高分子降解中產生的自由基，而且在光穩定化過程中具有再生功能，從而抑制連鎖反應，在本發明的較佳實施例中，紫外線吸收劑選自受阻胺類光安定劑(Hindered Amine Light Stabilizer，簡稱HALS)、羥基苯基苯并三唑類(benzotriazole)紫外線吸收劑或羥基二苯甲酮類(hydroxybenzophenone)紫外線吸收劑之中的一種或兩種以上的組合。另一方面，填充劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~30 PHR，其選自如碳酸鈣、粘土、滑石粉、碳酸鈣、雲母粉、石灰石以及矽石粉之中的一種或兩種以上。 The auxiliary agent is one of a ultraviolet absorber and a filler, or is used in combination. Among them, the content of the ultraviolet absorbent is 0.1 to 3 PHR relative to the polyolefin composition resin of 100 PHR. Its role is to eliminate free radicals generated during the irradiation of ultraviolet light, thereby preventing chain growth and reducing photodegradation or photooxidation. happened. Generally, it is a hindered amine compound. After the hindered amine absorbs light energy in an aerobic state, it can be converted into the corresponding nitroxide radical, thereby capturing the free radicals generated during the degradation of the polymer, and has a regeneration function in the process of light stabilization In order to suppress the chain reaction, in a preferred embodiment of the present invention, the ultraviolet absorber is selected from the group consisting of Hindered Amine Light Stabilizer (HALS), hydroxyphenylbenzotriazole (benzotriazole) ultraviolet absorber One or a combination of two or more of the hydroxybenzophenone (hydroxybenzophenone) ultraviolet absorber. On the other hand, the content of the filler is 0.1 to 30 PHR relative to the polyolefin composition resin of 100 PHR, which is selected from one of calcium carbonate, clay, talc, calcium carbonate, mica powder, limestone, and silica powder or More than two.

有關滑劑的特性，以及本發明較佳實施例中所選用的滑劑，在後文相關段落再進一步詳述。 The characteristics of the lubricant and the lubricant used in the preferred embodiment of the present invention will be further detailed in the relevant paragraphs below.

抗氧化劑可選自酚類抗氧化劑以及亞磷酸三苯酯類(Triphenyl phosphite)等，有時使用兩種或兩種以上的抗氧劑，可以產生明顯的協同效應。其中，酚類抗氧化劑能阻止鏈的增長， 並且能夠利用空間位阻效應阻止氧化反應的進行；亞磷酸三苯酯類則能與氧原子形成穩定的化合物，並分解氫過氧化物，且能終止自由基鏈反應，從而阻止鏈式反應的發生。 Antioxidants can be selected from phenolic antioxidants and triphenyl phosphites, etc. Sometimes two or more antioxidants are used, which can produce significant synergistic effects. Among them, phenolic antioxidants can prevent chain growth, and can use steric hindrance effects to prevent the oxidation reaction; triphenyl phosphite can form stable compounds with oxygen atoms, and decompose hydroperoxides, and can Stop the free radical chain reaction, thus preventing the chain reaction from occurring.

色料可視產品的色相需求酌予添加。實際使用上可採用有機色料、無機色料或採無機、有機色料混合的方式進行添加，如無特別需求也可以不加色料(即0 PHR)。色料可選自碳黑、鈦白(TiO2)、酞青綠、酞青藍、鈷藍、酮紅、汞鎘紅、鎘黃、鉻黃、偶氮黃、鉻綠、群青、Fe2O3褐等。由於微米級TiO2(0.1μm以上)具有強效的遮避力，因此除了可以作為色料用途外，適量添加之下還可以提高聚烯烴膜的反射率，而有助於提高太陽能電池對於光線能量的轉換效率，而能增進太陽能電池的發電效率；再者，添加適量的微米級TiO2還能夠提高聚烯烴膜的耐侯性，以提升太陽能電池的使用壽命；此外，微米級TiO2還可以強力吸收交聯劑，促使交聯劑均勻分散於樹脂內，進而避免在產品中出現焦黑點，有助於整體產品質量的提升。 Colorants can be added as appropriate depending on the hue requirements of the product. In actual use, it can be added by organic color, inorganic color or mixed inorganic and organic color. If there is no special demand, it can be added without color (ie 0 PHR). The colorant may be selected from carbon black, titanium white (TiO 2 ), phthalocyanine green, phthalocyanine blue, cobalt blue, ketone red, mercury cadmium red, cadmium yellow, chrome yellow, azo yellow, chrome green, ultramarine blue, Fe 2 O 3 brown and so on. Because micron-sized TiO 2 (more than 0.1 μm) has a strong hiding power, in addition to being used as a coloring material, the addition of an appropriate amount can improve the reflectivity of a polyolefin film and help improve the solar cell's resistance to light. Energy conversion efficiency can improve the efficiency of solar cell power generation. In addition, the addition of an appropriate amount of micron-sized TiO 2 can also improve the weatherability of polyolefin films to improve the life of solar cells. In addition, micron-sized TiO 2 can also Strongly absorb the cross-linking agent, promote the uniform dispersion of the cross-linking agent in the resin, thereby avoiding the occurrence of black spots in the product, and help improve the overall product quality.

回到本發明較佳實施例的流程步驟，在前述步驟S100中，首先將聚烯烴組合物樹脂、氟樹脂以及前述各種添加劑加入混合機中，並且在低溫條件下進行預攪拌以形成一混合物。接下來，以捏合機在低於交聯劑分解溫度的低溫下，均勻混煉混合物(步驟S102)。 Returning to the process steps of the preferred embodiment of the present invention, in the foregoing step S100, first, a polyolefin composition resin, a fluororesin, and the aforementioned various additives are added to a mixer, and pre-stirring is performed at a low temperature to form a mixture. Next, the mixture is uniformly kneaded with a kneader at a low temperature lower than the decomposition temperature of the crosslinking agent (step S102).

混合物經由捏合機充分捏合混煉後，被送入一軋輪機，以便能通過軋輪機使混合物初步膠化及交聯(步驟S104)。此時，為了使交聯劑發揮作用，將軋輪機的作業溫度控制在130至220℃(視所選用的交聯劑而定)之間。 After the mixture is sufficiently kneaded and kneaded through a kneader, it is sent to a rolling mill so that the mixture can be preliminarily gelled and crosslinked by the rolling mill (step S104). At this time, in order to make the cross-linking agent work, the working temperature of the rolling mill is controlled between 130 and 220 ° C (depending on the cross-linking agent selected).

當混合物在軋輪機中被初步膠化及交聯後，將膠化後的混合物以一壓延機製成一片體(步驟S106)。此時，將壓延機的作業溫度控制在130至220℃之間，可使得混合物在被壓延機壓延成片體的過程中，繼續發生膠化及交聯反應，進而使所製成的產品因為 經過充分地膠化與交聯，而具備良好的物性。具體而言，在此一步驟中可以採取較前一步驟更高的溫度，以助交聯劑分解，進而能促進交聯反應的進行。此外，將壓延機產出片體的產速控制在10~100公尺/每分鐘，且將片體的厚度控制在0.05mm至1.0mm之間，也有助於確保產品具備均勻且充分的交聯度。 After the mixture is preliminarily gelled and crosslinked in a rolling mill, the gelled mixture is formed into a single body by a calender (step S106). At this time, the working temperature of the calender is controlled between 130 and 220 ° C, so that the mixture continues to gel and crosslink during the process of being calendered into a sheet by the calender. After fully gelling and crosslinking, it has good physical properties. Specifically, in this step, a higher temperature than that in the previous step can be adopted to facilitate the decomposition of the cross-linking agent, which can further promote the progress of the cross-linking reaction. In addition, controlling the production rate of the sheet produced by the calender at 10 to 100 meters per minute, and controlling the thickness of the sheet between 0.05mm and 1.0mm, also helps to ensure that the product has a uniform and sufficient delivery.联 度。 Degree.

值得特別一提的是，在將本發明的膠片應用於其他不同用途時，可視實際需求對膠片進行壓印，此時，可將壓延機所製成的片體引入一壓花輪組，以通過壓花輪組於片體上壓製所需的紋路。由於本較佳實施例主要是以應用於太陽能電池背板為例，原則上可以不經過此壓印步驟，然而，如果為了提高反射效率而需要在片體的表面上形成光學微結構，也可選擇性地進行前述壓印步驟。 It is worth mentioning in particular that when the film of the present invention is applied to other different uses, the film can be embossed according to actual needs. At this time, the sheet body made by the calender can be introduced into an embossing wheel group to pass The embossing wheel set presses the required texture on the sheet body. Since this preferred embodiment is mainly applied to a solar cell backsheet as an example, in principle, this imprinting step may not be performed. However, if it is necessary to form an optical microstructure on the surface of the sheet in order to improve the reflection efficiency, The aforementioned embossing step is selectively performed.

另一方面，由於聚烯烴材料在高溫熔融狀態下粘度提高，因此在加工成型的過程中，容易發生粘輪的現象，並導致扭力增大而難以進行加工。為了避免前述狀況發生，本發明的較佳實施例添加適量的滑劑，且採用內、外部滑劑配合的方式。其中，偏外部滑劑包括C12~18脂肪酸系、脂肪酸酯系，以硬脂酸為佳；內外部兼具之滑劑包括脂肪酸醯胺類、金屬石鹼類、有機矽系之滑劑；內部滑劑包括C20以上脂肪酸、石蠟烴系等。本實施例利用上述不同內、外部特性的滑劑之搭配，使聚烯烴樹脂不與膠布機金屬輪面相粘，且聚烯烴樹脂間易與滑劑相容及膠化。如同前述，在本發明的較佳實施例中，滑劑的含量相對於100 PHR的聚烯烴組合物樹脂為0.1~15 PHR。其中，外部滑劑佔滑劑總量的40%~70%，其餘30%~60%則為內部滑劑或內外部兼具之滑劑。 On the other hand, since the viscosity of the polyolefin material is increased in a high-temperature molten state, during the process of molding, the phenomenon of sticking wheels easily occurs, and the torque is increased, making it difficult to process. In order to avoid the foregoing situation, the preferred embodiment of the present invention adds a proper amount of lubricant, and uses a combination of internal and external lubricants. Among them, partial external lubricants include C12-18 fatty acid and fatty acid esters, and stearic acid is preferred; internal and external lubricants include fatty acid amidoamines, metal alkaloids, and silicone-based lubricants; Internal lubricants include C20 or higher fatty acids, paraffin hydrocarbons, and the like. In this embodiment, the combination of the above-mentioned different internal and external lubricants is used to prevent the polyolefin resin from sticking to the metal wheel surface of the blanket machine, and the polyolefin resin is easily compatible and gelled with the lubricant. As mentioned above, in the preferred embodiment of the present invention, the content of the lubricant is 0.1 to 15 PHR relative to the polyolefin composition resin of 100 PHR. Among them, the external lubricant accounts for 40% to 70% of the total lubricant, and the remaining 30% to 60% are internal lubricants or both internal and external lubricants.

附帶一提的是，為了避免交聯聚烯烴在膠布機大表面輥壓時，積料(BANK)發生靜電火花，也可以考慮在一開始的混合物中加入抗靜電劑，藉此賦予聚烯烴樹脂表面導電化，以消除火花。具體來說可以採用乙氧基甘油脂肪酸酯類、磷酸鹽酯類、脂肪胺 類衍生物及其它醇類衍生物如烷類磷酸酯、聚乙二醇-硬脂酸酯其中的一種或兩種以上的相互配合，做為本發明的抗靜電劑使用。 Incidentally, in order to avoid static sparking of the BANK when the cross-linked polyolefin is rolled on the large surface of the blanket machine, it is also possible to consider adding an antistatic agent to the initial mixture to give the polyolefin resin. The surface is electrically conductive to eliminate sparks. Specifically, one or two of ethoxyglycerin fatty acid esters, phosphate esters, fatty amine derivatives, and other alcohol derivatives such as alkyl phosphates and polyethylene glycol-stearate can be used. The above interactions are used as the antistatic agent of the present invention.

回到本發明的主要流程步驟，在通過壓延機製成片體後，將片體引入冷卻輪組中，以使片體能夠充分冷卻定型(步驟S108)，並將最終製品捲曲收納，即完成本發明交聯耐候聚烯烴膠片的製備程序。 Returning to the main process steps of the present invention, after the sheet body is made by the calender, the sheet body is introduced into a cooling wheel set so that the sheet body can be sufficiently cooled and shaped (step S108), and the final product is curled and stored, which is completed. The preparation procedure of the crosslinked weather-resistant polyolefin film of the present invention.

[評價項目] [Evaluation item]

表1中列出本發明較佳實施例與市售氟膜的測試比較，其中，本發明較佳實施例的各種物性評估，分別採用下列測試方法進行評估： Table 1 lists the test comparison between the preferred embodiment of the present invention and the commercially available fluorine film. Among them, various physical property evaluations of the preferred embodiment of the present invention are evaluated by the following test methods:

1、破壞電壓(kV)以及介電強度(kV)：採用ASTM D149介質擊穿電壓強度測試進行評估。 1. Breakdown voltage (kV) and dielectric strength (kV): Evaluation is made by using ASTM D149 dielectric breakdown voltage strength test.

2、體積阻抗(Ω*cm)：採用ASTM D257體積/表面電阻測試。 2. Volume impedance (Ω * cm): Adopt ASTM D257 volume / surface resistance test.

3、伸長率(%)：採用ASTM D638M測試規格，以拉伸之速度測試，主要記錄為極限強度與應力應變圖。 3. Elongation (%): It adopts ASTM D638M test specifications and tests at the speed of elongation, which is mainly recorded as the ultimate strength and stress-strain diagram.

4、水氣透過率(g/M2/24hr)：採用ASTM F1249標準，在37.8℃和100%相對溼度條件下進行測試。 4. Water vapor transmission rate (g / M2 / 24hr): Tested under the conditions of 37.8 ℃ and 100% relative humidity using ASTM F1249 standard.

此外，表2中列出本發明較佳實施例與市售氟膜的耐候測試評估比較，具體採用了耐候測試儀(QUV，UVB 313燈管)，放置1000hrs、2000hrs、3000hrs以及4000hrs後，分別採用下列測試方法進行評估： In addition, Table 2 lists the comparison between the weatherability test evaluation of the preferred embodiment of the present invention and the commercially available fluorine film. Specifically, a weather resistance tester (QUV, UVB 313 lamp) was used. After being placed for 1000hrs, 2000hrs, 3000hrs, and 4000hrs, respectively, The following test methods were used for evaluation:

1、批內色差值(△b)：依GB/T 3979-2008標準測試其色差變化。 1. In-batch color difference value (△ b): Test its color difference change according to GB / T 3979-2008 standard.

2、黃變指數(Yellowness difference，△Y)：依ASTM E313-05標準測試其色差變化。 2. Yellowness index (Yellowness difference, △ Y): Test its color difference according to ASTM E313-05.

3、拉伸強度及撕裂強度：依ASTM D-882標準測試伸長率。 3. Tensile strength and tear strength: Test elongation according to ASTM D-882.

[實施例的有益效果] [Advantageous Effects of the Embodiment]

本發明的其中一有益效果在於，本發明所提供的交聯耐候聚烯烴膠片及其製法，其能通過“添加相對於100 PHR的聚烯烴組合物樹脂含量為0.2~5 PHR的氟樹脂”的技術方案，使得所製成的交聯耐候聚烯烴膠片具備良好的耐候特性，相較於現有技術直接以純氟樹脂製成的膠片的技術方案，本發明不但能夠以較低的成本達到同樣優異的耐候特性，此外，更具備相較於現有技術更佳的拉伸性。 One of the beneficial effects of the present invention is that the cross-linked weather-resistant polyolefin film provided by the present invention and the method for preparing the same can pass the "addition of a fluororesin with a resin content of 0.2 to 5 PHR relative to the polyolefin composition of 100 PHR". The technical solution makes the manufactured cross-linked weather-resistant polyolefin film have good weather resistance characteristics. Compared with the technical solution of a film made of pure fluorine resin directly in the prior art, the present invention can not only achieve the same excellent performance at a lower cost. In addition to weather resistance, it also has better stretchability than the prior art.

以上所公開的內容僅為本發明的優選可行實施例，並非因此侷限本發明的申請專利範圍，所以凡是運用本發明說明書及附圖內容所做的等效技術變化，均包含於本發明的申請專利範圍內。 The content disclosed above is only the preferred and feasible embodiment of the present invention, and therefore does not limit the scope of patent application of the present invention. Therefore, any equivalent technical changes made by using the description and drawings of the present invention are included in the application of the present invention. Within the scope of the patent.

Claims (11)

一種用於太陽電池背板的交聯耐候聚烯烴膠片，其包含聚烯烴組合物樹脂以及氟樹脂，其特徵在於，所述氟樹脂的含量相對於100重量份的所述聚烯烴組合物樹脂為0.2~5重量份，所述氟樹脂選自聚偏二氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物、聚三氟氯乙烯以及乙烯-聚三氟氯乙烯共聚物之中的一種或兩種以上的組合。     A cross-linked weather-resistant polyolefin film for a solar cell back sheet, comprising a polyolefin composition resin and a fluororesin, wherein the content of the fluororesin relative to 100 parts by weight of the polyolefin composition resin is 0.2 ~ 5 parts by weight, the fluororesin is selected from one of polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene, and ethylene-polytrifluorochloroethylene copolymer Or a combination of two or more.     如請求項1所述的交聯耐候聚烯烴膠片，還包含：交聯劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~5重量份，所述交聯劑為有機過氧化物交聯劑；交聯助劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0~2重量份，其選自二終端碳-碳雙鍵之二烯烴、二終端碳-碳雙鍵之三烯烴、二終端碳-碳雙鍵之四烯烴、三烯丙基異三聚氰酸酯、三羥甲基丙烷三丙烯酸酯以及奈米級二氧化鈦之中的一種或兩種以上的組合；滑劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~15重量份；助劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~80重量份；抗氧化劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~5重量份，其選自酚類抗氧劑或亞磷酸三苯酯類抗氧劑；以及色料，其含量相對於100重量份的所述聚烯烴組合物樹脂為0~25重量份。     The cross-linked weather-resistant polyolefin film according to claim 1, further comprising: a cross-linking agent whose content is 0.1 to 5 parts by weight relative to 100 parts by weight of the polyolefin composition resin, and the cross-linking agent is organic Peroxide crosslinking agent; crosslinking assistant, the content of which is 0 to 2 parts by weight relative to 100 parts by weight of the polyolefin composition resin, which is selected from the group consisting of di-terminal carbon-carbon double bonds diolefins, di-terminals One or two of carbon-carbon double bond triolefins, two-terminal carbon-carbon double bond tetraolefins, triallyl isocyanurate, trimethylolpropane triacrylate, and nanoscale titanium dioxide A combination of more than one kind; a slip agent whose content is 0.1 to 15 parts by weight relative to 100 parts by weight of the polyolefin composition resin; an auxiliary agent whose content is 0.1 relative to 100 parts by weight of the polyolefin composition resin ~ 80 parts by weight; an antioxidant in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the polyolefin composition resin, which is selected from phenolic antioxidants or triphenyl phosphite antioxidants; and The content of the colorant is 0 to 25 parts by weight based on 100 parts by weight of the polyolefin composition resin.     如請求項2所述的交聯耐候聚烯烴膠片，其中，所述助劑為紫 外線吸收劑以及填充劑之中的一種或混合並用；其中，所述填充劑的含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~30重量份；其中，所述紫外線吸收劑的含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~3重量份，其選自受阻胺類光安定劑、羥基苯基苯并三唑類紫外線吸收劑或羥基二苯甲酮類紫外線吸收劑之中的一種或兩種以上的組合。     The cross-linked weather-resistant polyolefin film according to claim 2, wherein the auxiliary agent is one or a combination of an ultraviolet absorber and a filler; wherein the content of the filler is relative to 100 parts by weight of the polymer. The polyolefin composition resin is 0.1 to 30 parts by weight; wherein the content of the ultraviolet absorber is 0.1 to 3 parts by weight relative to 100 parts by weight of the polyolefin composition resin, which is selected from hindered amine light stabilizers. Agent, hydroxyphenylbenzotriazole-based ultraviolet absorber, or hydroxybenzophenone-based ultraviolet absorber, or a combination of two or more.     如請求項1所述的交聯耐候聚烯烴膠片，其中，所述聚烯烴組合物樹脂選自聚乙烯、聚丙烯以及乙烯-醋酸乙烯酯共聚合物之中的兩種或兩種以上的組合。     The cross-linked weather-resistant polyolefin film according to claim 1, wherein the polyolefin composition resin is selected from two or more combinations of polyethylene, polypropylene, and ethylene-vinyl acetate copolymers .     如請求項4所述的交聯耐候聚烯烴膠片，其中，所述聚烯烴組合物樹脂，包含以下組成成分：聚乙烯，其含量為20至50重量份，所述聚乙烯為乙烯均聚物，或乙烯和具有3至12個碳原子的α-烯烴的共聚物；聚丙烯，其含量為30至60重量份，所述聚丙烯為丙烯均聚物與丙烯和一種或多種其它α-烯烴的共聚物，其中丙烯的聚合物部分至少占共聚物重量的60%；以及乙烯-醋酸乙烯酯共聚合物，其含量為0.1至30重量份，所述乙烯-醋酸乙烯酯共聚合物中醋酸乙烯酯的含量佔乙烯-醋酸乙烯酯共聚合物總量的8~33%。     The cross-linked weather-resistant polyolefin film according to claim 4, wherein the polyolefin composition resin contains the following constituent components: polyethylene, the content of which is 20 to 50 parts by weight, and the polyethylene is an ethylene homopolymer , Or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms; polypropylene, which contains 30 to 60 parts by weight, the polypropylene is a propylene homopolymer with propylene and one or more other α-olefins A copolymer in which the polymer portion of propylene accounts for at least 60% by weight of the copolymer; and an ethylene-vinyl acetate copolymer having a content of 0.1 to 30 parts by weight of acetic acid in the ethylene-vinyl acetate copolymer The content of vinyl ester accounts for 8 ~ 33% of the total ethylene-vinyl acetate copolymer.     如請求項1所述的交聯耐候聚烯烴膠片，其中，所述氟樹脂為分子量介於25萬至100萬的聚四氟乙烯。     The crosslinked weather-resistant polyolefin film according to claim 1, wherein the fluororesin is polytetrafluoroethylene having a molecular weight of 250,000 to 1 million.     如請求項1所述的交聯耐候聚烯烴膠片，其中，所述交聯耐候聚烯烴膠片對波長介於420至650nm的光線反射率大於65%。     The cross-linked weather-resistant polyolefin film according to claim 1, wherein the cross-linked weather-resistant polyolefin film has a reflectance of light having a wavelength between 420 and 650 nm of more than 65%.     一種用於太陽電池背板的交聯耐候聚烯烴膠片的製法，其包括下列步驟：將聚烯烴組合物樹脂以及氟樹脂以混合機進行預攪拌以形成一混合物，其中，所述氟樹脂含量相對於100重量份的所述聚烯烴組合物樹脂為0.2~5重量份；以一捏合機對所述混合物進行均勻混煉；以一軋輪機使所述混合物的成分進行膠化及交聯；將膠化後的所述混合物以一壓延機製成一片體；以及將所述片體引入冷卻輪組冷卻定型。     A method for manufacturing a cross-linked weather-resistant polyolefin film for a solar cell back sheet, comprising the following steps: pre-stirring a polyolefin composition resin and a fluororesin with a mixer to form a mixture, wherein the content of the fluororesin is relatively The polyolefin composition resin at 100 parts by weight is 0.2 to 5 parts by weight; the mixture is uniformly kneaded by a kneader; the ingredients of the mixture are gelatinized and crosslinked by a rolling mill; The gelatinized mixture is made into one piece by a calender; and the piece is introduced into a cooling wheel set for cooling and setting.     如請求項8所述的交聯耐候聚烯烴膠片的製法，其中，在進行預攪拌以形成所述混合物的步驟中，還混合有：交聯劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~5重量份，所述交聯劑為有機過氧化物交聯劑；交聯助劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0~2重量份，其選自二終端碳-碳雙鍵之二烯烴、三烯烴化合物、四烯烴化合物、三烯丙基異三聚氰酸酯、三羥甲基丙烷三丙烯酸酯以及奈米級二氧化鈦之中的一種或兩種以上的組合；滑劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~15重量份；助劑，其含量相對於100重量份的所述聚烯烴組合物樹脂為0.1~80重量份；以及色料，其含量相對於100重量份的所述聚烯烴組合物樹脂為0~35重量份。     The method for producing a cross-linked weather-resistant polyolefin film according to claim 8, wherein, in the step of performing pre-stirring to form the mixture, a cross-linking agent is further mixed with a content of 100 parts by weight of the polymer. The olefin composition resin is 0.1 to 5 parts by weight, and the cross-linking agent is an organic peroxide cross-linking agent; the cross-linking assistant has a content of 0 to 2 parts by weight relative to 100 parts by weight of the polyolefin composition resin. It is selected from the group consisting of diolefins, triolefin compounds, tetraolefin compounds, triallyl isotricyanates, trimethylolpropane triacrylates, and nano-grade titanium dioxide with two terminal carbon-carbon double bonds. A combination of one or two or more; a slip agent whose content is 0.1 to 15 parts by weight relative to 100 parts by weight of the polyolefin composition resin; an auxiliary agent whose content is relative to 100 parts by weight of the polyolefin combination The resin is 0.1 to 80 parts by weight; and the colorant has a content of 0 to 35 parts by weight relative to 100 parts by weight of the polyolefin composition resin.     如請求項8所述的交聯耐候聚烯烴膠片的製法，其中，所述軋 輪機以及所述壓延機作業的溫度控制在130至220℃之間。     The method for producing a cross-linked weather-resistant polyolefin film according to claim 8, wherein the operating temperature of the rolling mill and the calender is controlled between 130 and 220 ° C.     如請求項8所述的交聯耐候聚烯烴膠片的製法，其中，所述氟樹脂為平均粒徑介於3至10μm的粉末，且所述氟樹脂為分子量介於25萬至100萬的聚四氟乙烯。     The method for producing a cross-linked weather-resistant polyolefin film according to claim 8, wherein the fluororesin is a powder having an average particle diameter of 3 to 10 μm, and the fluororesin is a polymer having a molecular weight of 250,000 to 1 million. Tetrafluoroethylene.    
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