TW201511310A - Rearside protective sheet for solar cell module - Google Patents
Rearside protective sheet for solar cell module Download PDFInfo
- Publication number
- TW201511310A TW201511310A TW103124200A TW103124200A TW201511310A TW 201511310 A TW201511310 A TW 201511310A TW 103124200 A TW103124200 A TW 103124200A TW 103124200 A TW103124200 A TW 103124200A TW 201511310 A TW201511310 A TW 201511310A
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- resin
- solar cell
- cell module
- protective sheet
- Prior art date
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
本發明關於一種太陽能電池模組用背面保護片，進一步詳細而言，關於一種即使暴露於高溫-高濕度環境下或在高溫-低溫間的溫度變化之後，與太陽能電池模組內部的填充材片的密著仍然優異的太陽能電池模組用背面保護片。 The present invention relates to a back protective sheet for a solar cell module, and more particularly to a filler sheet inside a solar cell module even after exposure to a high temperature-high humidity environment or a temperature change between a high temperature and a low temperature. The back of the solar cell module is still excellent with a back protective sheet.
近年來，由於對環境問題的意識提高，作為綠色能源的太陽光發電正受到矚目，已有開發並提出由各種形態所構成的太陽能電池模組。一般而言，太陽能電池模組是藉由使用結晶矽太陽能電池元件或無定形矽太陽能電池元件等的光電元件，依序積層表面保護片、乙烯-乙酸乙烯酯共聚物樹脂等的填充材片、太陽能電池元件、填充材片、及背面保護片層，進行真空吸引並且熱壓接而一體化的方法來製造。構成太陽能電池模組的背面保護片，一般是採用輕量，電氣特性/強度優異的塑膠基材，從輕量性、防濕性與高耐電壓特性來考量，逐漸使用聚烯烴系樹脂薄膜。為了將聚烯烴系樹脂薄膜使用於太陽能電池模組用背面保護片的構件，必須解決聚烯烴系樹脂薄膜特有的課題，因此有了各種提案。例如在專利文獻1、2中，揭示了特定聚烯烴系樹脂薄膜與雙 軸延伸聚對苯二甲酸乙二酯薄膜積層而成的太陽能電池模組用背面保護片。 In recent years, solar power generation as a green energy source has been attracting attention due to an increase in awareness of environmental issues, and solar cell modules composed of various forms have been developed and proposed. In general, a solar cell module is formed by sequentially laminating a surface protective sheet or a filler sheet such as an ethylene-vinyl acetate copolymer resin by using a photovoltaic element such as a crystalline germanium solar cell element or an amorphous germanium solar cell element. The solar cell element, the filler sheet, and the back surface protective sheet layer are produced by vacuum suction and thermocompression bonding. The back surface protective sheet constituting the solar cell module is generally made of a lightweight plastic material having excellent electrical properties and strength. The polyolefin resin film is gradually used in consideration of light weight, moisture resistance, and high withstand voltage characteristics. In order to use a polyolefin-based resin film for a member of a back surface protective sheet for a solar cell module, it is necessary to solve the problem specific to the polyolefin-based resin film. Therefore, various proposals have been made. For example, in Patent Documents 1 and 2, a specific polyolefin resin film and a double are disclosed. A back protective sheet for a solar cell module in which a shaft-extending polyethylene terephthalate film is laminated.
太陽能電池模組用背面保護片能夠由背面以 機械的方式保護太陽能電池模組，同時具有防止水蒸氣的滲入或紫外線造成之劣化的機能，為了使背面保護片長期發揮其機能，被要求與填充材片堅固接著的特性。因此，認証機關會對於太陽能電池模組實施高溫高濕試驗(85℃ 85%RH)、結露凍結試驗(85℃ 85%RH與-40℃的重覆)以作為長期信賴性試驗。為了對應這些試驗，太陽能電池模組廠商重視長期信賴性試驗後之與填充材片的密著強度。 The back protection sheet for the solar cell module can be The solar cell module is mechanically protected, and has a function of preventing the infiltration of water vapor or the deterioration of ultraviolet rays. In order to make the back protective sheet exhibit its function for a long period of time, it is required to be firmly adhered to the filler sheet. Therefore, the certification authority will perform a high-temperature and high-humidity test (85 °C 85% RH) and a dew condensation test (85 °C 85% RH and -40 °C) for the solar cell module as a long-term reliability test. In order to cope with these tests, solar cell module manufacturers pay attention to the adhesion strength of the filler sheet after the long-term reliability test.
專利文獻3、4、5所記載的發明，其目的為提升填充材片與背面保護片的密著性，然而暴露於高溫-高濕度的環境後的密著性並不充足。 In the inventions described in Patent Documents 3, 4, and 5, the purpose of the invention is to improve the adhesion between the filler sheet and the back sheet, but the adhesion after exposure to a high-temperature-high humidity environment is not sufficient.
專利文獻1 日本特開2011-51124號公報 Patent Document 1 Japanese Patent Laid-Open Publication No. 2011-51124
專利文獻2 日本特開2013-201155號公報 Patent Document 2 Japanese Patent Laid-Open Publication No. 2013-201155
專利文獻3 日本特開2006-152013號公報 Patent Document 3 Japanese Patent Laid-Open Publication No. 2006-152013
專利文獻4 日本特開2003-060218號公報 Patent Document 4 Japanese Patent Laid-Open Publication No. 2003-060218
專利文獻5 國際公開第2012/043248號 Patent Document 5 International Publication No. 2012/043248
本發明鑑於上述先前技術的問題點而完成，目的為提供一種即使暴露於在高溫-高濕度的環境及高溫-低溫間的溫度變化，與填充材片之乙烯-乙酸乙烯酯共聚物樹脂片的密著性仍然優異的太陽能電池模組用背面保護片。 The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide an ethylene-vinyl acetate copolymer resin sheet with a filler sheet even when exposed to a high temperature-high humidity environment and a temperature change between a high temperature and a low temperature. A back protective sheet for solar cell modules that is still excellent in adhesion.
本發明為一種太陽能電池模組用背面保護片，其係聚烯烴系樹脂薄膜與塑膠薄膜積層而成的太陽能電池模組用背面保護片，其特徵為：前述聚烯烴系樹脂薄膜係包含至少A層/B層的2層以上，A層係包含(a)聚乙烯系樹脂及(b)聚丙烯系樹脂，塑膠薄膜側的B層係包含聚丙烯系樹脂，(b)聚丙烯系樹脂的熔點在145℃以下的範圍。 The present invention is a back surface protective sheet for a solar cell module, which is a back surface protective sheet for a solar cell module in which a polyolefin resin film and a plastic film are laminated, wherein the polyolefin resin film contains at least A. Two or more layers of the layer/B layer, the layer A includes (a) a polyethylene resin and (b) a polypropylene resin, and the B layer on the plastic film side contains a polypropylene resin, and (b) a polypropylene resin. The melting point is in the range of 145 ° C or less.
本發明可提供一種太陽能電池模組用背面保護片，其係即使暴露於高溫-高濕度的環境下或高溫-低溫間的溫度變化，與填充材片之乙烯-乙酸乙烯酯共聚物樹脂(以下會有簡稱為EVA的情形)片的密著性仍然優異。 The present invention can provide a back surface protective sheet for a solar cell module, which is an ethylene-vinyl acetate copolymer resin (hereinafter referred to as a filler sheet) even when exposed to a high temperature-high humidity environment or a high temperature-low temperature temperature change. There will be a case where the film is abbreviated as EVA. The adhesion of the sheet is still excellent.
以下針對本發明詳細說明。 The invention is described in detail below.
本發明為一種太陽能電池模組用背面保護片，其係聚烯烴系樹脂薄膜與塑膠薄膜積層而成的太陽 能電池模組用背面保護片，其特徵為：前述聚烯烴系樹脂薄膜係包含至少A層/B層的2層以上之聚烯烴系樹脂薄膜，並且A層係包含(a)聚乙烯系樹脂及(b)聚丙烯系樹脂，塑膠薄膜側的B層係包含聚丙烯系樹脂，(b)聚丙烯系樹脂的熔點在145℃以下的範圍。 The present invention relates to a back protective sheet for a solar cell module, which is a solar system in which a polyolefin resin film and a plastic film are laminated. The back surface protective sheet for a battery module, characterized in that the polyolefin-based resin film contains at least two or more polyolefin-based resin films of the A layer/B layer, and the A layer contains (a) a polyethylene resin. And (b) a polypropylene resin, the B layer on the plastic film side contains a polypropylene resin, and (b) the polypropylene resin has a melting point of 145 ° C or less.
本發明中的聚烯烴系樹脂薄膜係包含至少A層/B層的2層的構成之聚烯烴系樹脂薄膜。亦即A層/B層、或A層/B層/C層為代表性的例子，而A層/B層的2層構成是必須的，可因應必要進一步增加積層數至4層以上。聚烯烴系樹脂薄膜的A層主要目的為確保與填充材片的密著力，B層主要目的為確保耐熱性。 The polyolefin-based resin film of the present invention is a polyolefin-based resin film comprising at least two layers of A layer/B layer. That is, the A layer/B layer, or the A layer/B layer/C layer is a representative example, and the two layer configuration of the A layer/B layer is necessary, and it is necessary to further increase the number of layers to four or more layers as necessary. The main purpose of the layer A of the polyolefin-based resin film is to secure adhesion to the filler sheet, and the main purpose of the layer B is to ensure heat resistance.
在本發明中，聚烯烴系樹脂薄膜的A層的(a)聚乙烯系樹脂的熔點係以在100~130℃的範圍為較佳。若將熔點定在100℃以上，則在與填充材片熱壓接時，背面保護片的厚度不易減低，容易確保耐電壓特性。若為130℃以下，則與填充材片的密著強度的提升效果優異。 In the present invention, the (a) polyethylene-based resin of the A layer of the polyolefin-based resin film preferably has a melting point of from 100 to 130 °C. When the melting point is set to 100 ° C or more, the thickness of the back surface protective sheet is not easily reduced when the pressure-sensitive adhesive sheet is thermocompression bonded, and it is easy to ensure the withstand voltage characteristics. When it is 130 ° C or less, the effect of improving the adhesion strength of the filler sheet is excellent.
在本發明中，聚烯烴系樹脂薄膜的A層所使用的(a)聚乙烯系樹脂，可列舉高壓法低密度聚乙烯、直鏈狀低密度聚乙烯、高密度聚乙烯、或該等的混合樹脂。其中，直鏈狀低密度聚乙烯為較佳。 In the present invention, the (a) polyethylene-based resin used in the layer A of the polyolefin-based resin film may, for example, be a high-pressure method low-density polyethylene, a linear low-density polyethylene, a high-density polyethylene, or the like. Mixed resin. Among them, linear low density polyethylene is preferred.
直鏈狀低密度聚乙烯(以下會有簡稱為LLDPE的情形)是指乙烯與α-烯烴的共聚物，以碳原子數4~20，較佳為4~8的α-烯烴的共聚物為更佳，具體而言，可列舉與1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己 烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯等的共聚物。這些α-烯烴可單獨或組合使用，從聚合生產性而言，尤其1-丁烯、1-己烯、1-辛烯等較適合使用。 The linear low-density polyethylene (hereinafter referred to as LLDPE for short) means a copolymer of ethylene and an α-olefin, and a copolymer of an α-olefin having 4 to 20 carbon atoms, preferably 4 to 8 carbon atoms is used. More preferably, specific examples thereof include 1-butene, 1-pentene, 4-methyl-1-pentene, and 1-hexene. a copolymer of an ene, 1-heptene, 1-octene, 1-decene, 1-decene or the like. These α-olefins may be used singly or in combination, and from the viewpoint of polymerization productivity, especially 1-butene, 1-hexene, 1-octene and the like are preferably used.
在本發明中，聚烯烴系樹脂薄膜的A層的(b)聚丙烯系樹脂的熔點在145℃以下是重要的。若超過145℃，則與填充材片的密著力會不足，尤其是本發明的課題之對高溫-高濕下、高溫-低溫間的溫度變化的密著力之降低顯著。此外，A層的(b)聚丙烯系樹脂的熔點係以在120~140℃的範圍為佳。藉由將熔點定在120℃以上，A層的耐熱性充足，作為背面保護片與填充材片熱壓接時，不易發生背面保護片的厚度之部分性降低，容易確保耐電壓特性。另外，藉由將熔點定在140℃以下，與填充材片的密著強度可更加堅固。 In the present invention, the (b) polypropylene resin of the A layer of the polyolefin resin film has a melting point of 145 ° C or less. When the temperature exceeds 145 ° C, the adhesion to the filler sheet is insufficient, and in particular, the adhesion of the temperature change between high temperature to high humidity and high temperature to low temperature is remarkable. Further, the melting point of the (b) polypropylene resin of the layer A is preferably in the range of 120 to 140 °C. When the melting point is set to 120 ° C or higher, the heat resistance of the layer A is sufficient, and when the back surface protective sheet and the filler sheet are thermocompression bonded, the thickness of the back surface protective sheet is less likely to be partially lowered, and the withstand voltage characteristics are easily secured. Further, by setting the melting point to 140 ° C or lower, the adhesion strength to the filler sheet can be made stronger.
在本發明中，聚烯烴系樹脂薄膜的A層的(b)聚丙烯系樹脂係以選自乙烯-丙烯隨機共聚物、乙烯-丙烯-丁烯隨機共聚物、乙烯-丙烯嵌段共聚物的至少一種以上的樹脂為佳，而其中熔點低的乙烯-丙烯隨機共聚物或乙烯-丙烯-丁烯隨機共聚物為更佳。 In the present invention, the (b) polypropylene-based resin of the A layer of the polyolefin-based resin film is selected from the group consisting of an ethylene-propylene random copolymer, an ethylene-propylene-butene random copolymer, and an ethylene-propylene block copolymer. At least one or more resins are preferred, and an ethylene-propylene random copolymer or an ethylene-propylene-butene random copolymer having a low melting point is more preferable.
在本發明中，聚烯烴系樹脂薄膜的A層，係以上述(a)聚乙烯系樹脂相對於(b)聚丙烯系樹脂的重量組成比(a)/(b)在0.2~0.6的範圍為佳，在0.30~0.55的範圍為較佳。藉由將(a)/(b)定在0.6以下，與EVA片的密著強度會變得更堅固。在本發明中，由於B層是由聚丙烯系樹脂所構成，(a)/(b)在0.6以下則A層中的聚丙烯系樹脂的比例會變大，容易充分確保與B層的密著 性。在A層僅為聚乙烯系樹脂的情況，A層與B層間容易剝離。另一方面，若將(a)/(b)定在0.2以上並將聚乙烯系樹脂的比例定在一定的值以上，則在聚丙烯系樹脂中聚乙烯系樹脂會微分散，在A層表面產生凹凸，這樣容易使薄膜彼此的潤滑性良好。 In the present invention, the A layer of the polyolefin resin film has a weight composition ratio (a)/(b) of the (a) polyethylene resin to the (b) polypropylene resin in the range of 0.2 to 0.6. Preferably, it is preferably in the range of 0.30 to 0.55. By setting (a)/(b) below 0.6, the adhesion strength to the EVA sheet becomes stronger. In the present invention, the B layer is composed of a polypropylene resin, and when (a)/(b) is 0.6 or less, the ratio of the polypropylene resin in the A layer is increased, and it is easy to sufficiently ensure the adhesion to the B layer. the Sex. In the case where the layer A is only a polyethylene resin, the layer A and the layer B are easily peeled off. On the other hand, when (a)/(b) is set to 0.2 or more and the ratio of the polyethylene-based resin is set to a predetermined value or more, the polyethylene-based resin is slightly dispersed in the polypropylene-based resin, and is in the layer A. Concavities and convexities are formed on the surface, so that the lubricity of the films is easily improved.
若上述(a)/(b)為0.2~0.6的範圍，則容易抑制在85℃ 85%RH下1000小時的高溫高濕試驗後，以及在85℃ 85%RH下處理20小時後在-40℃下處理30分鐘的循環實施20次循環的結露凍結試驗後之與填充材片的密著強度降低。 When the above (a)/(b) is in the range of 0.2 to 0.6, it is easy to suppress the high temperature and high humidity test at 1000 ° C for 8 hours at 85 ° C and 8 hours after treatment at 85 ° C and 85% RH for 40 hours. The cycle of treatment for 30 minutes at ° C was carried out for 20 cycles, and the adhesion strength to the filler sheet was lowered after the condensation freeze test for 20 cycles.
另外，藉由將(a)/(b)定在0.2~0.6的範圍，A層側與經熱壓接之EVA片的初期密著強度為60N/cm以上，120℃ 100%RH條件下48小時後，以及在120℃ 100%RH條件下96小時後的密著強度成為40N/cm以上，而較佳。藉由將初期密著強度定在60N/cm以上，對於太陽能電池模組之施工時的各種機械的應力可容易保證充分的耐性，藉由將120℃ 100%RH條件下48小時後，及120℃ 100%RH條件下96小時後的密著強度定在40N/cm以上，可抑制太陽能電池模組長期使用時的剝離所造成的問題。 Further, by setting (a)/(b) in the range of 0.2 to 0.6, the initial adhesion strength of the A layer side and the thermocompression bonded EVA sheet is 60 N/cm or more, and 120 ° C 100% RH condition 48 After the hour, and the adhesion strength after 96 hours at 120 ° C and 100% RH is 40 N/cm or more, it is preferable. By setting the initial adhesion strength to 60 N/cm or more, it is easy to ensure sufficient resistance to various mechanical stresses during the construction of the solar cell module by using 120 ° C under 100% RH for 48 hours, and 120 °C The adhesion strength after 96 hours under 100% RH conditions is set at 40 N/cm or more, which can suppress the problems caused by peeling of the solar cell module during long-term use.
在本發明中，聚烯烴系樹脂薄膜的A層，係以上述(a)聚乙烯系樹脂相對於(b)聚丙烯系樹脂的重量組成比(a)/(b)在0.30~0.55的範圍為更佳。若(a)/(b)為此範圍，則容易抑制在85℃ 85%RH下1000小時的高溫高濕試驗後，及在85℃ 85%RH下20小時後在-40℃下處 理30分鐘的循環實施20次循環的結露凍結試驗後之與填充材片的密著強度降低。本發明中，A層的表面平均粗糙度Ra為0.10~0.30μm，由於可滿足加工時薄膜的操作性，故為較佳。另外，為了改善薄膜的操作性、潤滑性，亦可在本發明中的A層，相對於A層的樹脂成分，添加0.1~10重量%之平均粒徑1~5μm的無機或有機粒子。此外還可相對於A層樹脂成分，添加0.1~10重量%之有機化合物的潤滑劑。有機化合物的潤滑劑可列舉硬脂酸醯胺、硬脂酸鈣等。 In the present invention, the A layer of the polyolefin resin film has a weight composition ratio (a)/(b) of the (a) polyethylene resin to the (b) polypropylene resin in the range of 0.30 to 0.55. For better. If (a)/(b) is in this range, it is easy to suppress after 1000 hours of high temperature and high humidity test at 85 ° C 85% RH, and at -40 ° C after 20 hours at 85 ° C 85% RH. The 30-minute cycle was carried out for 20 cycles of the condensation freeze test, and the adhesion strength to the filler sheet was lowered. In the present invention, the surface average roughness Ra of the layer A is from 0.10 to 0.30 μm, which is preferable because it can satisfy the workability of the film during processing. Further, in order to improve the handleability and lubricity of the film, in the layer A of the present invention, 0.1 to 10% by weight of inorganic or organic particles having an average particle diameter of 1 to 5 μm may be added to the resin component of the layer A. Further, a lubricant of 0.1 to 10% by weight of an organic compound may be added to the resin component of the layer A. Examples of the lubricant of the organic compound include decylamine stearate, calcium stearate, and the like.
在本發明中，聚烯烴系樹脂薄膜的B層係包含聚丙烯系樹脂組成物，尤其從耐熱性的觀點而言，比A層所使用的聚丙烯系樹脂組成物熔點更高且熔點為140~170℃的同元聚丙烯、乙烯-丙烯嵌段共聚物較適合使用。B層亦可混合聚乙烯系樹脂，而從耐熱性的觀點而言，其含量未滿B層樹脂成分全體的30重量%為更佳。 In the present invention, the B layer of the polyolefin-based resin film contains a polypropylene-based resin composition, and particularly has a higher melting point and a melting point of 140 than the polypropylene-based resin composition used in the layer A from the viewpoint of heat resistance. The isotactic polypropylene and ethylene-propylene block copolymer of ~170 ° C are suitable for use. The B layer may be mixed with a polyethylene resin, and from the viewpoint of heat resistance, the content is preferably less than 30% by weight based on the entire B layer resin component.
於本發明之太陽能電池模組用背面保護片，藉由在聚烯烴系樹脂薄膜的B層及/或塑膠薄膜添加各種著色劑而賦予隱蔽性，由於可保持太陽能電池模組用背面保護片全體的隱蔽性，故較佳。 In the back surface protective sheet for a solar cell module of the present invention, the coloring agent is added to the B layer and/or the plastic film of the polyolefin resin film to provide concealability, and the back protective sheet for the solar cell module can be held. The concealment is better.
另外如前述般，在本發明中的聚烯烴系樹脂薄膜的B層亦可添加著色劑，尤其是白化劑。從耐候性的觀點而言，白化劑以碳酸鈣、二氧化矽、氧化鋁、氫氧化鎂、氧化鋅、滑石、高嶺土、氧化鈦、硫酸鋇等的無機系的微粒子為佳，其中以氧化鈦粒子為最佳，作為結晶型雖已知有金紅石型、銳鈦礦型、板鈦礦型等，但 從優異的白色度與耐候性及光反射性等的特性而言，以金紅石型為佳。 Further, as described above, a coloring agent, particularly a whitening agent, may be added to the layer B of the polyolefin-based resin film of the present invention. From the viewpoint of weather resistance, the whitening agent is preferably inorganic fine particles such as calcium carbonate, cerium oxide, aluminum oxide, magnesium hydroxide, zinc oxide, talc, kaolin, titanium oxide or barium sulfate, of which titanium oxide is used. The particles are optimal, and as the crystal form, rutile type, anatase type, brookite type, etc. are known, but The rutile type is preferred from the viewpoints of excellent whiteness, weather resistance, and light reflectivity.
在對B層使用白化劑的情況，藉由將聚烯烴系樹脂薄膜設計成A層/B層/C層的3層構成，並以A層及C層夾住含有白化劑的B層，可抑制大量含有白化劑的樹脂分解物附著在製造時的金屬嘴，可避免分解物脫落所造成的步驟污染、薄膜損傷之品質問題。 When a whitening agent is used for the layer B, the polyolefin resin film is designed to have a three-layer structure of the A layer/B layer/C layer, and the layer B containing the whitening agent is sandwiched between the A layer and the C layer. It is possible to prevent the resin decomposition product containing a large amount of whitening agent from adhering to the metal nozzle at the time of manufacture, and it is possible to avoid the problem of step contamination and film damage caused by the decomposition of the decomposition product.
在本發明中，在聚烯烴系樹脂薄膜積層C層的情況，C層係以包含聚丙烯系樹脂組成物為較佳。C層與B層同樣地包含聚丙烯系樹脂，以包含選自同元聚丙烯、乙烯-丙烯隨機共聚物、乙烯-丙烯-丁烯隨機共聚物、乙烯-丙烯嵌段共聚物的至少一種以上的樹脂、或該等的樹脂與聚乙烯系樹脂的混合樹脂為佳。尤其從首先是耐熱性，再來潤滑性或薄膜的操作性、耐刮傷性、耐彎曲性的觀點而言，以嵌段共聚物為最佳，從耐熱性再加上潤滑性或薄膜的操作性、耐刮傷性、耐彎曲性的觀點而言，其熔點係以140~170℃的範圍為佳。藉由將熔點定在140℃以上，耐熱性優異，在作為太陽能電池模組用背面保護片與EVA片熱壓接時，太陽能電池模組用背面保護片的厚度不會因為溫度與壓力而部分性減低，可保持耐電壓特性，故較佳。 In the present invention, in the case where the polyolefin resin film is laminated with the C layer, the C layer is preferably a polypropylene resin composition. The C layer and the B layer contain a polypropylene resin in an amount of at least one selected from the group consisting of a homopolypropylene, an ethylene-propylene random copolymer, an ethylene-propylene-butene random copolymer, and an ethylene-propylene block copolymer. The resin or a mixed resin of the resin and the polyethylene resin is preferred. In particular, from the viewpoint of heat resistance first, lubricity, film workability, scratch resistance, and bending resistance, block copolymers are preferred, and heat resistance plus lubricity or film is added. From the viewpoints of workability, scratch resistance, and bending resistance, the melting point is preferably in the range of 140 to 170 °C. When the melting point is set to 140 ° C or higher, the heat resistance is excellent. When the back surface protective sheet for a solar cell module is thermocompression bonded to the EVA sheet, the thickness of the back surface protective sheet for the solar cell module is not partially due to temperature and pressure. It is preferable because it has low resistance and can maintain voltage withstand characteristics.
進一步還可在C層混合聚乙烯系樹脂，但從耐熱性的觀點而言，其含量係以未滿C層樹脂成分全體的30重量%為較佳。 Further, the polyethylene resin may be mixed in the layer C. However, from the viewpoint of heat resistance, the content is preferably 30% by weight based on the total of the resin component of the C layer.
從防止各層變色、維持強度的觀點而言，本發明中的聚烯烴系樹脂薄膜係以添加周知的抗氧化劑為較佳。抗氧化劑已知有酚系、芳香族胺系、硫醚系、磷系等，為了以少量摻合來提高效果，以併用2種以上為更佳。例如以併用酚系與磷系為佳，可列舉磷-酚系抗氧化劑。 The polyolefin-based resin film of the present invention is preferably added with a well-known antioxidant from the viewpoint of preventing discoloration of each layer and maintaining strength. The oxidizing agent is known to have a phenol type, an aromatic amine type, a thioether type, a phosphorus type, etc., and it is preferable to use two or more types in combination in order to improve the effect by mixing in a small amount. For example, a phenol type and a phosphorus type are preferably used in combination, and a phosphorus-phenol type antioxidant is mentioned.
上述其他添加劑可列舉光安定劑、紫外線吸收劑、熱安定劑。光安定劑可採用捕捉樹脂中之光劣化起始的活性種，防止光氧化的物質。具體而言，可使用選自受阻胺系化合物、受阻哌啶系化合物、及其他等的1種或組合兩種以上者。其中以使用受阻胺系化合物為較佳。 Examples of the other additives include a photosensitizer, an ultraviolet absorber, and a heat stabilizer. The light stabilizer can be used to prevent photo-oxidation of the active species which initiate photodegradation in the resin. Specifically, one type or a combination of two or more types selected from the group consisting of a hindered amine compound, a hindered piperidine compound, and the like can be used. Among them, a hindered amine compound is preferably used.
上述紫外線吸收劑可採用能夠吸收太陽光中的有害紫外線並在分子內轉換成無害的熱能，防止樹脂中的光劣化起始的活性種受到激發的物質。具體而言，可使用選自包含二苯酮系、苯并***系、柳酸酯系、丙烯酸腈系、金屬錯鹽系、受阻胺系、及超微粒子氧化鈦(粒徑：0.01μm~0.06μm)或超微粒子氧化鋅(粒徑：0.01μm~0.04μm)等的無機系等的紫外線吸收劑之群組中的至少1種以上。 The above ultraviolet absorbing agent may be one which is capable of absorbing harmful ultraviolet rays in sunlight and converting it into harmless thermal energy in the molecule, and preventing active species which are initiated by photodegradation in the resin from being excited. Specifically, a benzophenone-based, benzotriazole-based, salicylic acid-based, acrylonitrile-based, metal-salt-based, hindered amine-based, and ultrafine titanium oxide (particle size: 0.01 μm~) can be used. At least one or more of the group of ultraviolet absorbers such as inorganic particles, such as 0.06 μm) or ultrafine zinc oxide (particle diameter: 0.01 μm to 0.04 μm).
另外，上述熱安定劑可列舉參(2,4-二-三級丁基苯基)亞磷酸酯、雙[2,4-雙(1,1-二甲基乙基)-6-甲基苯基]乙基酯亞磷酸、肆(2,4-二-三級丁基苯基)[1,1-聯苯基]-4,4'-二基雙亞膦酸酯、及雙(2,4-二-三級丁基苯基)新戊四醇二亞磷酸酯等的磷系熱安定劑、8-羥基-5,7-二- 三級丁基-呋喃-2-酮與鄰二甲苯的反應生成物等的內酯系熱安定劑。另外，該等可使用1種或2種以上。其中，以併用磷系熱安定劑及內酯系熱安定劑來使用為更佳。 Further, examples of the above thermal stabilizer include ginseng (2,4-di-tertiary butylphenyl) phosphite and bis[2,4-bis(1,1-dimethylethyl)-6-methyl. Phenyl]ethyl ester phosphorous acid, ruthenium (2,4-di-tert-butylphenyl) [1,1-biphenyl]-4,4'-diyl bisphosphonite, and bis ( Phosphorus thermal stabilizer such as 2,4-di-tertiary butylphenyl neopentaerythritol diphosphite, 8-hydroxy-5,7-di- A lactone-based thermal stabilizer such as a reaction product of a tertiary butyl-furan-2-one and o-xylene. In addition, one type or two or more types can be used. Among them, it is more preferable to use a phosphorus-based heat stabilizer and a lactone-based heat stabilizer.
另外，本發明中的聚烯烴系樹脂薄膜可因應必要添加阻燃劑。阻燃劑並未受到特別限定，可適用有機阻燃劑、無機阻燃劑等周知技術。作為有機阻燃劑的例子為在分子中含有1個以上的氯原子或溴原子的物質，可列舉例如氯化石蠟、氯化聚乙烯、六氯內亞甲基四氫酞酸、全氯五環癸烷、四氯化酞酸酐等、或參(2,3-二溴丙基)異氰尿酸酯等的具有芳香環且在該芳香環並沒有鹵素原子直接鍵結的單體或聚合物、1,1,2,2-四溴乙烷、1,4-二溴丁烷、1,3-二溴丁烷、1,5-二溴戊烷、α-溴酪酸乙酯、1,2,5,6,9,10-六溴環癸烷等的不具有芳香環的物質。 Further, the polyolefin-based resin film in the present invention may contain a flame retardant as necessary. The flame retardant is not particularly limited, and a well-known technique such as an organic flame retardant or an inorganic flame retardant can be applied. Examples of the organic flame retardant include those having one or more chlorine atoms or bromine atoms in the molecule, and examples thereof include chlorinated paraffin, chlorinated polyethylene, hexachloromethylenetetrahydrofurfuric acid, and perchloroacetic acid. a monomer or polymerization having an aromatic ring such as cyclodecane, tetradecylic acid anhydride or the like, or bis(2,3-dibromopropyl)isocyanurate and having no halogen atom directly bonded to the aromatic ring. , 1,1,2,2-tetrabromoethane, 1,4-dibromobutane, 1,3-dibromobutane, 1,5-dibromopentane, α-bromobutyric acid ethyl ester, 1 A substance having no aromatic ring such as 2,5,6,9,10-hexabromocyclodecane.
另外，作為無機阻燃劑的例子可列舉氫氧化鋁、氫氧化鎂等的氫氧化無機鹽、磷酸銨、磷酸鋅等的磷氧化物、紅磷、三氧化銻或膨脹石墨等。 Further, examples of the inorganic flame retardant include a hydroxide inorganic salt such as aluminum hydroxide or magnesium hydroxide, a phosphorus oxide such as ammonium phosphate or zinc phosphate, red phosphorus, antimony trioxide or expanded graphite.
有機阻燃劑及無機阻燃劑之單獨或混合物的摻合量係以相對於各層的樹脂為5~30重量%的範圍為佳。在添加量未滿5重量%的情況，沒有添加效果，若超過30重量%，則會有分散性惡化、阻燃劑所致之著色發生的情形。本發明之太陽能電池模組用背面保護片的聚烯烴系樹脂薄膜，係以由A層/B層或A層/B層/C層所構成為佳，其積層比不受特別限定，但以聚烯烴系樹脂薄膜為100%時，A層為5~20%、B層為95~60%、C層為0~20%的厚度構成比率範圍為較佳。 The blending amount of the organic flame retardant and the inorganic flame retardant alone or in a mixture is preferably in the range of 5 to 30% by weight based on the resin of each layer. When the amount of addition is less than 5% by weight, there is no effect of addition, and if it exceeds 30% by weight, the dispersibility is deteriorated and the coloring due to the flame retardant occurs. The polyolefin-based resin film for the back surface protective sheet for a solar cell module of the present invention is preferably composed of an A layer/B layer or an A layer/B layer/C layer, and the layering ratio thereof is not particularly limited, but When the polyolefin resin film is 100%, the thickness ratio of the A layer is 5 to 20%, the B layer is 95 to 60%, and the C layer is 0 to 20%.
在使用本發明中的聚烯烴系樹脂薄膜作為太陽能電池模組用背面保護片時，在與A層相反側積層塑膠薄膜來使用，以確保作為背面保護片所需的機械強度及長期耐久性。因此，對於本發明中的聚烯烴系樹脂薄膜與A層相反側實施表面改質處理為較佳。本發明中的表面改質處理，可列舉在大氣中的電暈放電處理、在氮氣環境下的電暈放電處理、電漿處理等，但只要是用於與塑膠薄膜接著的處理，則並不受該等所限定。 When the polyolefin-based resin film of the present invention is used as a back surface protective sheet for a solar cell module, a plastic film is laminated on the side opposite to the A layer to ensure mechanical strength and long-term durability required for the back surface protective sheet. Therefore, it is preferred that the polyolefin-based resin film of the present invention is subjected to surface modification treatment on the side opposite to the layer A. The surface modification treatment in the present invention includes corona discharge treatment in the air, corona discharge treatment in a nitrogen atmosphere, plasma treatment, etc., but it is not used for the subsequent treatment with the plastic film. Subject to such restrictions.
在本發明中，A層表面係以不實施改質處理為較佳。若A層及與A層相反側一起進行表面改質處理，則在薄膜的製造、及分條裁切步驟之中，薄膜彼此容易黏連(Blocking)，容易導致破裂、剝離帶電的問題、展開不良等的問題。甚至容易發生薄膜彼此的潤滑性變差，而損害積層或塗布等加工性等的問題。 In the present invention, it is preferred that the surface of the layer A is not subjected to upgrading treatment. When the surface layer is subjected to the surface modification treatment together with the layer A and the side opposite to the layer A, the film is easily bonded to each other during the production of the film and the slitting step, and the problem of cracking, peeling and charging is likely to occur. Bad problems. Even if the lubricity of the films deteriorates, the problems such as workability such as lamination or coating are impaired.
如前述般，在本發明中，由於A層表面的凹凸的形成狀況會隨著A層的(a)聚乙烯系樹脂相對於(b)聚丙烯系樹脂的重量組成比(a)/(b)而發生變化，影響到潤滑性，再加上上述A層的表面處理的影響，因此作為確認本發明的太陽能電池模組用背面保護片用的聚烯烴系樹脂薄膜的加工性的方法，一般是依照ASTM D1894-11e1並使用滑性試驗儀的摩擦試驗。A面與B面(A層/B層2層構成品)或A面與C面(A層/B層/C層3層構成品)的動摩擦係數未滿1.1時，潤滑性優異，加工時不會發生黏連或起波(Knocking)等的問題，而較佳。 As described above, in the present invention, the formation ratio of the unevenness on the surface of the layer A is proportional to the weight composition ratio of the (a) polyethylene resin to the (b) polypropylene resin of the layer A (a)/(b). And the method of determining the processability of the polyolefin-based resin film for the back surface protective sheet for a solar cell module of the present invention is generally a method of determining the processability of the surface treatment of the solar cell module of the present invention. It is a friction test in accordance with ASTM D1894-11e1 and using a slip tester. When the dynamic friction coefficient of the A surface and the B surface (A layer/B layer 2 layer component) or the A surface and the C surface (A layer/B layer/C layer 3 layer component) is less than 1.1, the lubricity is excellent, and during processing, It is preferable that problems such as adhesion or Knocking do not occur.
本發明中的塑膠薄膜可為單層，或可為多個薄膜貼合而成的多層薄膜。 The plastic film in the present invention may be a single layer or a multilayer film in which a plurality of films are laminated.
本發明中的塑膠薄膜為聚對苯二甲酸乙二酯(以下簡稱為PET)、聚萘二甲酸乙二酯(以下簡稱為PEN)等的聚酯薄膜；聚乙烯或聚丙烯等的聚烯烴薄膜；聚苯乙烯薄膜；聚醯胺薄膜；聚氯乙烯薄膜；聚碳酸酯薄膜；聚丙烯酸腈薄膜；聚醯亞胺薄膜；氟系樹脂薄膜等。從機械強度或耐熱性、經濟性的觀點而言，該等之中適合使用PET薄膜，從需要長期維持特性的觀點而言，以耐水解性PET薄膜為較佳。同樣地，因為可得到高耐水解性的理由，以PEN薄膜為佳。 The plastic film in the present invention is a polyester film of polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate (hereinafter referred to as PEN), or the like, and a polyolefin such as polyethylene or polypropylene. Film; polystyrene film; polyamide film; polyvinyl chloride film; polycarbonate film; polyacrylonitrile film; polyimine film; fluorine resin film. From the viewpoint of mechanical strength, heat resistance, and economy, a PET film is suitably used among them, and a hydrolysis-resistant PET film is preferable from the viewpoint of maintaining long-term characteristics. Similarly, a PEN film is preferred because of the high hydrolysis resistance.
另外，從耐候性的觀點而言，本發明中的塑膠薄膜係以氟系樹脂薄膜為佳，亦適合使用積層聚酯薄膜與氟系樹脂薄膜的薄膜。 Further, from the viewpoint of weather resistance, the plastic film of the present invention is preferably a fluorine-based resin film, and a film of a laminated polyester film and a fluorine-based resin film is also suitably used.
在本發明中，塑膠薄膜所適合採用的耐水解性PET薄膜，其在140℃高壓水蒸氣下保管10小時後的拉伸伸度保持在初期的拉伸伸度的60%以上。 In the present invention, the hydrolysis-resistant PET film suitable for use in a plastic film maintains the tensile elongation after storage for 10 hours under high-pressure steam at 140 ° C at 60% or more of the initial tensile elongation.
藉由使用耐水解性PET薄膜作為構成太陽能電池模組用背面保護片的塑膠薄膜，可大幅提升太陽能電池模組用背面保護後片的耐候性，有助於作為太陽能電池模組的10年以上的性能保證，而較佳。 By using a hydrolysis-resistant PET film as a plastic film constituting a back surface protective sheet for a solar cell module, the weather resistance of the back surface protective sheet for a solar cell module can be greatly improved, and it is useful as a solar cell module for more than 10 years. The performance guarantee is better.
作為耐水解性PET薄膜，市面上販售一種PET薄膜，其依據JIS C2151(1996)測定薄膜的破裂伸度時，與在140℃高壓水蒸氣條件下水蒸氣處理前作比較，50%伸度降低時間為不具有耐水解性的薄膜的2倍以 上，具體而言，東麗股份有限公司製的「Lumirror」(註冊商標)X10S等適合使用作為本發明中的塑膠薄膜。 As a hydrolysis-resistant PET film, a PET film is commercially available, and when it is determined according to JIS C2151 (1996), the elongation at break of the film is compared with that before the steam treatment under high-pressure steam at 140 ° C, and the elongation is 50%. 2 times that of a film that does not have hydrolysis resistance In particular, "Lumirror" (registered trademark) X10S manufactured by Toray Industries, Inc. is suitably used as the plastic film in the present invention.
本發明中的塑膠薄膜所適合採用的PEN薄膜，係將二羧酸成分採用2,6-萘二甲酸，二醇成分採用乙二醇並以周知方法聚合所形成的樹脂同樣地以周知方法進行雙軸延伸而成的薄膜。 The PEN film suitable for the plastic film of the present invention is a resin obtained by polymerizing a dicarboxylic acid component with 2,6-naphthalene dicarboxylic acid, and a diol component by ethylene glycol and polymerizing by a known method. A film that is biaxially stretched.
這些耐水解性PET薄膜或PEN薄膜的厚度係以38~300μm為佳，從薄膜的黏度的強度(剛性)、耐電壓性、太陽能電池模組用背面保護片的成本及太陽能電池模組製造時的加工適性而言，係以50~250μm為較佳。 The thickness of these hydrolysis-resistant PET film or PEN film is preferably 38 to 300 μm, and the strength (rigidity), withstand voltage of the film, the cost of the back surface protective sheet for a solar cell module, and the manufacture of the solar cell module. In terms of processing suitability, it is preferably 50 to 250 μm.
本發明中的塑膠薄膜所適合採用的氟系樹脂薄膜，係可使氟系樹脂熔融，由金屬嘴擠出成片狀，使其在旋轉冷卻滾筒上冷卻固化，而製成目標厚度的氟系樹脂薄膜。 The fluorine-based resin film suitable for the plastic film of the present invention is obtained by melting a fluorine-based resin, extruding it into a sheet shape from a metal nozzle, and cooling and solidifying it on a rotary cooling drum to produce a fluorine-based target. Resin film.
氟系樹脂可列舉聚氟乙烯、聚氟化亞乙烯、四氟乙烯-六氟丙烯-氟化亞乙烯共聚物、四氟乙烯-丙烯共聚物、四氟乙烯-六氟丙烯-丙烯共聚物、乙烯-四氟乙烯共聚物(ETFE)、六氟丙烯-四氟乙烯共聚物(FEP)、或全氟(烷基乙烯基醚)-四氟乙烯共聚物、聚氯三氟乙烯樹脂等。從製成薄膜的熔融擠出成形性的觀點而言，在這些氟樹脂之中，尤其以聚氟乙烯、乙烯-四氟乙烯共聚物(ETFE)、六氟丙烯-四氟乙烯共聚物(FEP)、全氟(烷基乙烯基醚)-四氟乙烯共聚物、聚氯三氟乙烯聚合物為佳。 Examples of the fluorine-based resin include polyvinyl fluoride, polyfluorinated ethylene, tetrafluoroethylene-hexafluoropropylene-vinylidene copolymer, tetrafluoroethylene-propylene copolymer, and tetrafluoroethylene-hexafluoropropylene-propylene copolymer. Ethylene-tetrafluoroethylene copolymer (ETFE), hexafluoropropylene-tetrafluoroethylene copolymer (FEP), perfluoro(alkyl vinyl ether)-tetrafluoroethylene copolymer, polychlorotrifluoroethylene resin, and the like. Among these fluororesins, in particular, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer (ETFE), hexafluoropropylene-tetrafluoroethylene copolymer (FEP) from the viewpoint of melt extrusion formability of the film to be formed A perfluoro(alkyl vinyl ether)-tetrafluoroethylene copolymer or a polychlorotrifluoroethylene polymer is preferred.
本發明中的塑膠薄膜所適合採用的氟系樹脂薄膜，藉由電暈放電處理、電漿處理、火焰處理、化學 處理等對表面實施活性化處理，可提升積層後的密著強度。 The fluorine-based resin film suitable for the plastic film of the present invention, by corona discharge treatment, plasma treatment, flame treatment, chemistry The surface is subjected to an activation treatment such as treatment to enhance the adhesion strength after lamination.
本發明中的塑膠薄膜，亦適合採用上述聚酯薄膜與氟系樹脂薄膜積層而成者。 The plastic film of the present invention is also suitably formed by laminating the above-mentioned polyester film and a fluorine-based resin film.
在本發明中，為了太陽能電池模組用背面保護片的長期耐候性，在塑膠薄膜與聚烯烴系樹脂薄膜積層的一側的相反側積層紫外線吸收層為較佳，此情況下，適合者可例示包含在丙烯酸系樹脂等的黏結劑樹脂中摻合紫外線吸收劑的樹脂組成物、或使丙烯酸系樹脂等與紫外線吸收劑及光安定化劑共聚合而成的樹脂者，但從與塑膠薄膜基材的密著性、或紫外線吸收層本身的耐候性的觀點而言，其中以包含使丙烯酸系樹脂等與紫外線吸收劑及光安定化劑共聚合而成的樹脂者為佳。 In the present invention, in order to have long-term weather resistance of the back surface protective sheet for a solar cell module, it is preferable to laminate an ultraviolet absorbing layer on the side opposite to the side on which the plastic film and the polyolefin resin film are laminated. In this case, it is suitable. The resin composition containing a UV absorber in a binder resin such as an acrylic resin or a resin obtained by copolymerizing an acrylic resin or the like with an ultraviolet absorber and a light stabilizer is exemplified, but a plastic film is used. From the viewpoint of the adhesion of the substrate or the weather resistance of the ultraviolet absorbing layer itself, it is preferred to include a resin obtained by copolymerizing an acrylic resin or the like with an ultraviolet absorber and a light stabilizer.
作為與丙烯酸系樹脂共聚合的紫外線吸收劑，可例示水楊酸系、二苯酮系、苯并***系、氰基丙烯酸酯系等的紫外線吸收劑。 The ultraviolet absorber which is copolymerized with the acrylic resin may, for example, be an ultraviolet absorber such as a salicylic acid, a benzophenone, a benzotriazole or a cyanoacrylate.
另外，與前述丙烯酸樹脂共聚合的光安定化劑，同樣地可列舉受阻胺系等的光安定化劑。 Further, similarly to the light stabilizer of the acrylic resin copolymerization, a light stabilizer such as a hindered amine system can be mentioned.
在紫外線吸收層添加白色顏料，由於可提升紫外線吸收層的樹脂的耐候性，故為佳，從泛用性、價格、發色性能，以及耐紫外線性的觀點而言，白色顏料係以氧化鈦為佳。 It is preferable to add a white pigment to the ultraviolet absorbing layer, and it is preferable to improve the weather resistance of the resin of the ultraviolet absorbing layer. From the viewpoint of versatility, price, color development property, and ultraviolet ray resistance, the white pigment is titanium oxide. It is better.
紫外線吸收層的厚度係以0.2~5μm為佳，更佳為1~4μm，特佳為1~3μm。藉由將紫外線吸收層的厚度定在0.2μm以上，在塗布時不會發生龜裂或膜 斷裂這些現象，而容易形成均勻的塗膜，可充分表現出對於塑膠薄膜特別是聚對苯二甲酸乙二酯薄膜的密著力，以及最重要的紫外線遮蔽性能，而為適合。另一方面，藉由使紫外線吸收層的厚度在5μm以下，可充分表現出紫外線遮蔽性能，若比此值更厚，則會對塗布方式造成限制，在生產成本變高等之點有所顧慮。在本發明中，塑膠薄膜與聚烯烴系樹脂薄膜的貼合所使用的黏著劑並未受到特別限定，但一般是使用異氰酸酯交聯型黏著劑。其中，為了製作出耐候性優異且接著力逐時降低小的太陽能電池模組用背面保護片，以使用耐水解性優異的黏著劑為佳。 The thickness of the ultraviolet absorbing layer is preferably 0.2 to 5 μm, more preferably 1 to 4 μm, and particularly preferably 1 to 3 μm. By setting the thickness of the ultraviolet absorbing layer to 0.2 μm or more, cracking or filming does not occur at the time of coating. By breaking these phenomena, it is easy to form a uniform coating film, and it is sufficient to sufficiently exhibit the adhesion to the plastic film, particularly the polyethylene terephthalate film, and the most important ultraviolet shielding performance. On the other hand, when the thickness of the ultraviolet absorbing layer is 5 μm or less, the ultraviolet shielding performance can be sufficiently exhibited, and if it is thicker than this value, the coating method is limited, and there is a concern that the production cost becomes high. In the present invention, the adhesive used for bonding the plastic film and the polyolefin-based resin film is not particularly limited, but an isocyanate cross-linking type adhesive is generally used. Among them, in order to produce a back surface protective sheet for a solar cell module which is excellent in weather resistance and which is subsequently reduced in strength, it is preferred to use an adhesive having excellent hydrolysis resistance.
上述黏著劑所使用的溶劑係以酯類、酮類、脂肪族類、芳香族類等的不具有活性氫的溶劑為佳。酯類可列舉醋酸乙酯、醋酸丙酯、醋酸丁酯等。酮類可列舉甲基乙基酮、甲基異丁基酮、環己酮等。脂肪族可列舉正庚烷、正己烷、環己烷等。芳香族類可列舉甲苯、二甲苯等。從溶解度、塗布適性的觀點而言，該等之中以醋酸乙酯、醋酸丙酯、甲基乙基酮為特佳。 The solvent used for the above-mentioned adhesive is preferably a solvent having no active hydrogen such as an ester, a ketone, an aliphatic or an aromatic. Examples of the esters include ethyl acetate, propyl acetate, and butyl acetate. Examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the aliphatic group include n-heptane, n-hexane, and cyclohexane. Examples of the aromatic group include toluene and xylene. From the viewpoint of solubility and coating suitability, ethyl acetate, propyl acetate, and methyl ethyl ketone are particularly preferred among these.
另外，由黏著劑所構成的層的厚度係以0.1~10μm為佳，從成本面及接著性的觀點而言，以2~6μm為較佳。本發明中的太陽能電池模組用背面保護片的具體的製造方法，可使用凹版-輥塗布法、反向塗布法、吻合塗布法、其他塗布法、或使用印刷法等塗布黏著劑的乾式積層等的手段，在作為塑膠薄膜的例如PET薄膜積層烯烴系樹脂薄膜。此時，該PET薄膜亦可因應 必要實施電暈處理、電漿處理等的用以提升接著性的表面處理。亦可在該PET薄膜與預先塗布黏著劑的一面相反側的一面，使用凹版-輥塗布法、反向塗布法、吻合塗布法、其他塗布法、或刷法等塗布黏著劑，而形成紫外線吸收層。接下來，將該PET薄膜的黏著劑塗布面與聚烯烴系樹脂薄膜的A層的相反側的一面貼合。 Further, the thickness of the layer composed of the adhesive is preferably 0.1 to 10 μm, and more preferably 2 to 6 μm from the viewpoint of cost surface and adhesion. The specific manufacturing method of the back surface protective sheet for a solar cell module of the present invention can be carried out by using a gravure-roll coating method, a reverse coating method, an anastomosis coating method, another coating method, or a dry laminate in which an adhesive is applied by a printing method or the like. For example, a film of an olefin-based resin film is deposited as a plastic film, for example, a PET film. At this point, the PET film can also respond It is necessary to perform surface treatment for improving adhesion by corona treatment, plasma treatment, or the like. The PET film may be coated with an adhesive by a gravure-roll coating method, a reverse coating method, an anastomosis coating method, another coating method, or a brush method on the side opposite to the surface on which the adhesive is applied in advance, thereby forming an ultraviolet ray absorption. Floor. Next, the adhesive-coated surface of the PET film was bonded to the opposite side of the layer A of the polyolefin-based resin film.
塑膠薄膜與聚烯烴系樹脂薄膜的密著強度係以2N/15mm以上為佳。若這些薄膜間的密著強度在2N/15mm以上，則可充分得到積層薄膜的層間強度，太陽能電池模組加工時或促進試驗等造成的層間剝離不易發生，以6N/15mm以上為較佳。 The adhesion strength between the plastic film and the polyolefin resin film is preferably 2 N/15 mm or more. When the adhesion strength between the films is 2 N/15 mm or more, the interlayer strength of the laminated film can be sufficiently obtained, and interlayer peeling due to the test or the promotion of the solar cell module is less likely to occur, and 6 N/15 mm or more is preferable.
以下藉由實施例對本發明作詳細說明。此外，各特性是藉由以下的方法測定、評估。 The invention will now be described in detail by way of examples. Further, each characteristic was measured and evaluated by the following method.
(1)EVA密著強度評估用太陽能電池模組，是在往太陽能電池模組用背面保護片的聚烯烴系樹脂薄膜的A面側與EVA片2相向的方向上，依序使太陽能電池模組用背面保護片/EVA片2(FirstEVA公司製，F806厚度450μm)/EVA片1(FirstEVA公司製，F806厚度450μm)/玻璃板積層，設置於NPC股份有限公司製的太陽能電池模組積層機(LM-50X50-S)之後，在真空時間5.5分鐘、控制時間1分鐘、壓延時間11.5分鐘、溫度148℃的條件下進行加熱壓接。壓接後，冷卻至室溫，而製作出評估用太陽能電池模組。對於聚烯烴系樹脂薄膜的長邊方向進行橫方向的密著強度(初期)的測定。由太陽 能電池模組用背面保護片側，以寬度10mm將背面保護片/EVA片層間剝離，在室溫條件下使用Orientec股份有限公司製Tensilon PTM-50，以剝離角度180°、剝離速度100mm/min進行剝離，測定密著強度。 (1) The solar cell module for evaluating the EVA adhesion strength is a solar cell module in the direction in which the A-side of the polyolefin-based resin film for the solar cell module back protective sheet faces the EVA sheet 2 in this order. Group back protective sheet/EVA sheet 2 (manufactured by FirstEVA Co., Ltd., F806 thickness: 450 μm) / EVA sheet 1 (manufactured by FirstEVA Co., Ltd., F806 thickness: 450 μm) / glass sheet laminate, solar cell module laminator manufactured by NPC Co., Ltd. After (LM-50X50-S), heating and pressure bonding were performed under conditions of a vacuum time of 5.5 minutes, a control time of 1 minute, a rolling time of 11.5 minutes, and a temperature of 148 °C. After crimping, it was cooled to room temperature to prepare a solar cell module for evaluation. The adhesion strength (initial) of the transverse direction in the longitudinal direction of the polyolefin resin film was measured. By the sun The back side protective sheet/EVA sheet layer was peeled off at a width of 10 mm on the back side protective sheet side of the battery module, and Tensilon PTM-50 manufactured by Orientec Co., Ltd. was used at room temperature, and the peeling angle was 180°, and the peeling speed was 100 mm/min. Peel off and measure the adhesion strength.
(2)高溫高濕試驗後的EVA密著強度 (2) EVA adhesion strength after high temperature and high humidity test
將前述評估用太陽能電池模組在85℃ 85%RH的高溫高濕環境下保管1000小時後，以及在120℃ 100%RH下保管48小時或保管96小時後，與上述同樣地進行剝離，並測定EVA密著強度。 The solar cell module for evaluation was stored in a high-temperature and high-humidity environment at 85° C. and 85% RH for 1,000 hours, and then stored at 120° C. and 100% RH for 48 hours or stored for 96 hours, and then peeled off in the same manner as described above. The EVA adhesion strength was measured.
(3)結露凍結試驗後的EVA密著強度 (3) EVA adhesion strength after condensation freeze test
對於前述評估用太陽能電池模組進行在85℃ 85%RH下處理20小時後在-40℃下處理30分鐘的循環實施20次循環的結露凍結處理後，與上述同樣地進行剝離，並測定EVA密著強度。 The solar cell module for evaluation was subjected to a dew condensation freezing treatment in which a cycle of treatment at 85 ° C, 85% RH for 20 hours, and a treatment at -40 ° C for 30 minutes was carried out for 20 cycles, and then peeling was performed in the same manner as above, and EVA was measured. Adhesion strength.
(4)熔點測定 (4) Determination of melting point
所使用的樹脂的熔點是使用示差掃描熱量計(島津製作所製，DSC-60)，以10℃/分鐘的速度升溫，將由20℃加熱至300℃時融解峰的最高峰溫度定為熔點。 The melting point of the resin to be used was measured by a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) at a rate of 10 ° C/min, and the highest peak temperature of the melting peak when heated from 20 ° C to 300 ° C was defined as the melting point.
(5)加工性評估 (5) Processability assessment
對於本發明中的聚烯烴系樹脂薄膜的A面與B面(A層/B層2層構成品)、或A面與C面(A層/B層/C層3層構成品)等，依據ASTM D1894-11e1並使用滑性試驗儀測定聚烯烴系樹脂薄膜的一個表面與另一個表面的動摩擦係數。由摩擦係數的結果進行下述判定，依照下述基準，將「△」以上判定為合格。 In the polyolefin-based resin film of the present invention, the A surface and the B surface (A layer/B layer 2 layer constituent product), or the A surface and the C surface (A layer/B layer/C layer 3 layer constituent product), etc. The coefficient of dynamic friction of one surface and the other surface of the polyolefin-based resin film was measured in accordance with ASTM D1894-11e1 using a slip tester. The following determination was made based on the result of the friction coefficient, and "△" or more was judged as pass according to the following criteria.
○：動摩擦係數未滿0.9 ○: Dynamic friction coefficient is less than 0.9
△：動摩擦係數為0.9以上未滿1.1 △: The dynamic friction coefficient is 0.9 or more and less than 1.1.
×：動摩擦係數為1.1以上。 ×: The dynamic friction coefficient is 1.1 or more.
(實施例1) (Example 1)
由A層/B層/C層的3層構成所構成的聚烯烴系樹脂薄膜，並且A層所使用的樹脂採用將作為(b)聚丙烯系樹脂的乙烯-丙烯-丁烯隨機共聚物(熔點128℃、乙烯含量7重量%、丁烯含量3重量%，將其簡稱為r-EPBC)72重量%、作為(a)聚乙烯系樹脂的直鏈狀低密度聚乙烯(熔點127℃、乙烯-1-丁烯共聚物，將其簡稱為LLDPE(C4))28重量%混合而成的樹脂。(a)/(b)的重量組成比為0.39。B層所使用的樹脂是採用相對於聚丙烯系樹脂的乙烯-丙烯隨機共聚物(熔點147℃、乙烯含量4重量%、將其簡稱為r-EPC(1))80重量%，混合r-EPC(1)40重量%與以主成分為矽、鋁、鋅等之中的1種或多種的無機氧化物實施表面處理並且平均粒徑為200nm的金紅石型氧化鈦(堺化學工業股份有限公司製FTR-700)60重量%以雙軸擠出機在240℃下熔融混練之後進行切粒所製造出的氧化鈦母粒(將其簡稱為氧化鈦MB)20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。C層所使用的樹脂是採用聚丙烯系樹脂的乙烯-丙烯嵌段共聚物(熔點160℃、乙烯含量7重量%，將其簡稱為b-PP)100重量%。將以這種方式準備的A層、B層、C層各層的各個樹脂供給至單軸熔融擠出機，分別使其在260℃下熔融，並導引至A層/B層/C層型的多流道型T模具，擠出至保持 在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風使其冷卻固化，而得到各層厚度構成比率為A層/B層/C層=20%/70%/10%且厚度為150μm的聚烯烴系樹脂薄膜。對此聚烯烴系樹脂薄膜的C層側在大氣中以23W．min/m2的電能量實施電暈放電處理，使C層表面的潤濕張力成為40mN/m，並且加以捲繞。 A polyolefin-based resin film composed of three layers of the A layer/B layer/C layer, and the resin used for the A layer is an ethylene-propylene-butene random copolymer which is (b) a polypropylene resin ( a linear low-density polyethylene (melting point of 128 ° C, an ethylene content of 7% by weight, a butene content of 3% by weight, abbreviated as r-EPBC) of 72% by weight, and a linear low-density polyethylene of (a) a polyethylene resin (melting point: 127 ° C, A resin obtained by mixing an ethylene-1-butene copolymer, which is simply referred to as LLDPE (C4) 28% by weight. The weight composition ratio of (a)/(b) was 0.39. The resin used in the layer B is an ethylene-propylene random copolymer (melting point 147 ° C, ethylene content 4% by weight, abbreviated as r-EPC (1)) 80% by weight with respect to the polypropylene resin, and mixing r- EPC (1) 40% by weight and rutile-type titanium oxide having a surface treatment of an inorganic oxide having one or more of ruthenium, aluminum, zinc and the like as a main component and having an average particle diameter of 200 nm 60% by weight of the company FTR-700) A resin obtained by melt-kneading at 240 ° C in a twin-screw extruder and then granulating the titanium oxide masterbatch (abbreviated as titanium oxide MB) by 20% by weight. The amount of titanium oxide added to the whitening agent was 12% by weight. The resin used in the layer C is an ethylene-propylene block copolymer (melting point: 160 ° C, ethylene content: 7% by weight, abbreviated as b-PP) of 100% by weight of a polypropylene resin. The respective resins of the layers A, B, and C prepared in this manner were supplied to a uniaxial melt extruder, respectively, and melted at 260 ° C, and guided to the A layer / B layer / C layer type. The multi-channel type T mold is extruded to a casting drum maintained at 30 ° C, and is cooled and solidified by blowing cold air of 25 ° C from the non-roller surface side, thereby obtaining a thickness ratio of each layer to layer A/B layer/C layer. A polyolefin-based resin film having a thickness of 150 μm of 20%/70%/10%. The C layer side of the polyolefin resin film was 23 W in the atmosphere. The electric energy of min/m 2 was subjected to corona discharge treatment so that the wetting tension of the surface of the layer C became 40 mN/m, and was wound.
將日本觸媒股份有限公司製的紫外線吸收劑及光安定化劑(HALS)與丙烯酸多元醇樹脂交聯而成的塗布劑“Hulls-hybrid"聚合物(註冊商標)BK1(固體成分濃度：40重量%、丙烯酸樹脂)與白化劑、可塑劑及溶劑一起混合，使用珠磨機使其分散，而得到固體成分濃度為50重量%的樹脂層形成用主劑塗料。 A coating agent "Hulls-hybrid" polymer (registered trademark) BK1 (solid content concentration: 40) obtained by crosslinking a UV absorber and a light stabilizer (HALS) manufactured by Nippon Shokubai Co., Ltd. and an acrylic polyol resin. The weight %, acrylic resin) was mixed with a whitening agent, a plasticizer, and a solvent, and it was disperse|distributed by the bead mill, and the base-coating agent for resin layer formation of the solid-
接下來，在以前述方法所得到的樹脂層形成用主劑塗料中，預先計算出與主劑塗料的重量比成為33/8之比的量來摻合異氰尿酸酯(Nurate)型六亞甲基二異氰酸酯樹脂的住化拜耳胺基甲酸酯股份有限公司製“Desmodur"(註冊商標)N3300(固體成分濃度：100重量%)，接下來，量取預先計算出使其成為固體成分濃度20重量%(樹脂固體成分濃度)的塗料的稀釋劑：醋酸正丙酯，並攪拌15分鐘，而藉此得到固體成分濃度20重量%(樹脂固體成分濃度)的紫外線吸收層形成用塗料。 Next, in the main-agent paint for forming a resin layer obtained by the above method, an amount of the ratio of the weight ratio of the main-agent paint to 33/8 is calculated in advance to blend the isocyanurate type (Nurate) type six. "Desmodur" (registered trademark) N3300 (solid content concentration: 100% by weight) manufactured by Bayeine Ammonium Co., Ltd., a methylene diisocyanate resin, and then measured in advance to make it a solid component The diluent of the coating material having a concentration of 20% by weight (resin solid content concentration): n-propyl acetate was stirred for 15 minutes to obtain a coating material for forming an ultraviolet absorbing layer having a solid content concentration of 20% by weight (resin solid content concentration).
此外，上述調整所使用的白化劑採用氧化鈦粒子(Tayca股份有限公司製JR-709)，可塑劑採用DIC股份有限公司製環氧系可塑劑(“Epocizer"W-121)。 Further, the whitening agent used for the above adjustment was titanium oxide particles (JR-709 manufactured by Tayca Co., Ltd.), and the plasticizer was an epoxy plasticizer ("Epocizer" W-121) manufactured by DIC Corporation.
準備作為塑膠薄膜的耐水解性雙軸延伸PET薄膜(東麗股份有限公司製“Lumirror"(註冊商標)X10S(125μm))。在此薄膜的一面，使用乾式積層機(岡崎機械工業股份有限公司製附單色印刷的乾式積層機OG/DL-130TA-AF)，塗布上述紫外線吸收層形成用塗料，在150℃下乾燥30秒鐘，使固體成分塗布厚度成為1μm而設置紫外線吸收層。 A hydrolysis-resistant biaxially stretched PET film ("Lumirror" (registered trademark) X10S (125 μm) manufactured by Toray Industries, Inc.) was prepared as a plastic film. On the one side of the film, the coating material for forming an ultraviolet absorbing layer was applied by a dry laminator (a dry laminator OG/DL-130TA-AF with monochromatic printing manufactured by Okazaki Machinery Co., Ltd.), and dried at 150 ° C. In the second, the solid content coating thickness was set to 1 μm to provide an ultraviolet absorbing layer.
接下來，藉由上述乾式積層機，在設置上述“Lumirror"X10S的紫外線吸收層的一面與相反面塗布異氰酸酯交聯型黏著劑(大日本油墨化學工業股份有限公司製，LX-903/KL-75=8/1)，使固體成分塗布厚度成為4μm，並使其乾燥，以60N/cm的夾持壓與前述聚烯烴系樹脂薄膜的C層側實施積層。 Next, an isocyanate cross-linking adhesive (LX-903/KL-manufactured by Dainippon Ink and Chemicals Co., Ltd.) was applied to one surface and the opposite surface of the ultraviolet absorbing layer of the above-mentioned "Lumirror" X10S by the dry laminator. 75 = 8 / 1), the solid content was applied to a thickness of 4 μm, and dried, and laminated on the C layer side of the polyolefin-based resin film at a nip of 60 N/cm.
在溫度40℃下使積層薄膜熟成72小時，促進黏著劑層的硬化反應，本發明之製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 The laminated film was aged at a temperature of 40 ° C for 72 hours to promote the hardening reaction of the adhesive layer, and the back protective sheet for a solar cell module was produced by the present invention. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例2) (Example 2)
將實施例1所記載的烯烴系樹脂薄膜的厚度，在使A層/B層/C層厚度比率與實施例1相同的狀態下變更為200μm，將作為塑膠薄膜的耐水解性雙軸延伸PET薄膜(東麗股份有限公司製“Lumirror"X10S)的厚度定為75μm，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 The thickness of the olefin-based resin film of the first embodiment was changed to 200 μm in the same manner as in the first embodiment, and the water-resistant biaxially stretched PET film was used as the plastic film (the thickness of the layer A/B layer/C layer) was changed to 200 μm. A back surface protective sheet for a solar cell module was produced in the same manner as in Example 1 except that the thickness of the "Lumirror" X10S) manufactured by Toray Industries, Inc. was 75 μm. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例3) (Example 3)
除去實施例1所記載的紫外線吸收層，並將塑膠薄膜變更為東麗股份有限公司製“Lumirror"耐水解性白色PET薄膜的MX11(75μm)，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 The same procedure as in Example 1 was carried out except that the ultraviolet absorbing layer described in Example 1 was replaced with the MX11 (75 μm) of the "Lumirror" hydrolysis-resistant white PET film manufactured by Toray Industries, Inc. Method A back protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例4) (Example 4)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用相對於乙烯-丙烯隨機共聚物(熔點135℃、乙烯含量6重量%、將其簡稱為r-EPC(2))77重量%混合LLDPE(C4)23重量%而成的樹脂，將(a)/(b)的重量組成比定為0.30，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In the polyolefin-based resin film of the first embodiment, the resin used in the layer A is a copolymer of ethylene-propylene (melting point: 135 ° C, ethylene content: 6% by weight, and simply referred to as r-EPC (2). )) A solar energy produced in the same manner as in Example 1 except that the resin composition of 23% by weight of LLDPE (C4) was mixed in an amount of 23% by weight, and the weight composition ratio of (a)/(b) was set to 0.30. Back protection sheet for battery modules. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例5) (Example 5)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用相對於r-EPC(2)65重量%混合LLDPE(C4)35重量%而成的樹脂，將(a)/(b)的重量組成比定為0.54，除此之外，以與實施例1同樣的方法製作出 太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In the polyolefin-based resin film of the first embodiment, the resin used in the layer A is a resin obtained by mixing 35 wt% of LLDPE (C4) with respect to 65 wt% of r-EPC (2), and (a) In the same manner as in Example 1, except that the weight composition ratio of (b) was set to 0.54. Back protection sheet for solar cell modules. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例6) (Example 6)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用相對於r-EPBC80重量%混合LLDPE(C4)20重量%而成的樹脂，將(a)/(b)的重量比率定為0.25，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 In the polyolefin-based resin film of the first embodiment, the resin used for the layer A is a resin obtained by mixing 20% by weight of LLDPE (C4) with respect to 80% by weight of r-EPBC, and (a)/(b) A back surface protective sheet for a solar cell module was produced in the same manner as in Example 1 except that the weight ratio was 0.25. The results of the evaluation are disclosed in Table 1. After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(實施例7) (Example 7)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用相對於r-EPBC60重量%混合LLDPE(C4)40重量%而成的樹脂，將(a)/(b)的重量比率定為0.67，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度為40N/cm以上。 In the polyolefin-based resin film of the first embodiment, the resin used in the layer A is a resin obtained by mixing 40% by weight of LLDPE (C4) with respect to 60% by weight of r-EPBC, and (a)/(b) A back surface protective sheet for a solar cell module was produced in the same manner as in Example 1 except that the weight ratio was 0.67. The results of the evaluation are disclosed in Table 1. After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was 40 N/cm or more.
(比較例1) (Comparative Example 1)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂，採用相對於代替r-EPBC的乙烯-丙烯隨機共聚物(熔點147℃、乙烯含量4重量%、將其簡稱為r-EPC(1))72重量%混合LLDPE(C4)28重量%而成的樹 脂，將(a)/(b)的重量組成比定為0.39，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。在初期，EVA密著強度為40N/cm以上，然而在高溫高濕試驗後，結露凍結試驗後，EVA密著強度未滿40N/cm而並不充足。 In the polyolefin-based resin film of the first embodiment, the resin used in the layer A is an ethylene-propylene random copolymer (melting point: 147 ° C, ethylene content: 4% by weight), which is abbreviated as a substitute for r-EPBC. a tree of r-EPC (1)) 72% by weight mixed with LLDPE (C4) 28% by weight A back surface protective sheet for a solar cell module was produced in the same manner as in Example 1 except that the weight composition ratio of (a)/(b) was changed to 0.39. The results of the evaluation are disclosed in Table 1. In the initial stage, the EVA adhesion strength was 40 N/cm or more. However, after the high temperature and high humidity test, after the condensation freeze test, the EVA adhesion strength was less than 40 N/cm, which was not sufficient.
(比較例2) (Comparative Example 2)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用相對於代替r-EPBC的同元聚丙烯(熔點160℃、將其簡稱為h-PP)70重量%混合直鏈狀低密度聚乙烯(LLDPE(C4))30重量%而成的樹脂，將(a)/(b)的重量組成比定為0.43，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In the polyolefin-based resin film of the first embodiment, the resin used in the layer A is mixed with 70% by weight of the homopolypropylene (melting point: 160 ° C, abbreviated as h-PP) instead of r-EPBC. In the same manner as in Example 1, except that the resin composition of the linear low-density polyethylene (LLDPE (C4)) was 30% by weight, and the weight composition ratio of (a)/(b) was 0.43. A back protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 1.
EVA密著強度在初期為40N/cm以上，然而在高溫高濕試驗、結露凍結試驗後，未滿40N/cm而並不充足。 The EVA adhesion strength was 40 N/cm or more at the initial stage. However, after the high temperature and high humidity test and the condensation freeze test, it was not sufficient to be less than 40 N/cm.
(比較例3) (Comparative Example 3)
在比較例1之中，A層所使用的樹脂採用相對於r-EPC(1)65重量%混合LLDPE(C4)35重量%而成的樹脂，將(a)/(b)的重量組成比定為0.54，除此之外，以與比較例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In Comparative Example 1, the resin used in the layer A was a resin obtained by mixing 35 wt% of LLDPE (C4) with respect to 65 wt% of r-EPC (1), and the weight composition ratio of (a)/(b) was used. A back surface protective sheet for a solar cell module was produced in the same manner as in Comparative Example 1, except that the amount was 0.54. The results of the evaluation are disclosed in Table 1.
EVA密著強度在初期為40N/cm以上，然而在高溫高濕試驗、結露凍結試驗後，未滿40N/cm而並不充足。 The EVA adhesion strength was 40 N/cm or more at the initial stage. However, after the high temperature and high humidity test and the condensation freeze test, it was not sufficient to be less than 40 N/cm.
(比較例4) (Comparative Example 4)
在實施例1所記載的聚烯烴系樹脂薄膜之中，A層所使用的樹脂採用LLDPE(C4)100重量%，除此之外，以與實施例1同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In the same manner as in Example 1, except that the resin used in the layer A was 100% by weight of LLDPE (C4), the resin used for the solar cell module was produced in the same manner as in Example 1. Back protection sheet. The results of the evaluation are disclosed in Table 1.
在初期、高溫高濕試驗、結露凍結試驗後，EVA密著強度未滿40N/cm而並不充足。 After the initial stage, high temperature and high humidity test, and dew condensation test, the EVA adhesion strength was less than 40 N/cm and was insufficient.
(實施例8) (Example 8)
A層所使用的樹脂採用相對於r-EPBC(熔點128℃)75重量%混合LLDPE(C4)25重量%而成的樹脂。(a)/(b)的重量組成比為0.33。B層所使用的樹脂採用相對於r-EPC(1)80重量%混合氧化鈦MB20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。 The resin used for the layer A was a resin obtained by mixing 25% by weight of LLDPE (C4) with respect to 75 wt% of r-EPBC (melting point: 128 ° C). The weight composition ratio of (a)/(b) was 0.33. The resin used for the layer B was a resin obtained by mixing 80% by weight of titanium oxide MB with 80% by weight of r-EPC (1). The amount of titanium oxide added to the whitening agent was 12% by weight.
將以這種方式準備的A層、B層各層的各個樹脂供給至單軸熔融擠出機，分別在260℃下使其熔融，導引至A層/B層型的多流道型的T模具，擠出至保持在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風使其冷卻固化，而得到各層厚度構成比率為A層/B層=20%/80%且厚度為150μm的聚烯烴系樹脂薄膜。 Each resin of each of the A layer and the B layer prepared in this manner was supplied to a uniaxial melt extruder, and melted at 260 ° C, respectively, and guided to a multi-channel type T of the A layer/B layer type. The mold was extruded to a casting drum maintained at 30 ° C, and cold air of 25 ° C was blown from the non-roller surface side to be solidified by cooling, and the thickness ratio of each layer was obtained as A layer / B layer = 20% / 80% and the thickness was A 150 μm polyolefin resin film.
對於此聚烯烴系樹脂薄膜的B層側在大氣中以23W．min/m2的電能量實施電暈放電處理，使B層表面的潤濕張力成為40mN/m，並且加以捲繞。 For the B-layer side of this polyolefin-based resin film, it is 23 W in the atmosphere. The electric energy of min/m 2 was subjected to corona discharge treatment so that the wetting tension of the surface of the layer B became 40 mN/m, and was wound.
準備作為塑膠薄膜的耐水解性雙軸延伸PET薄膜(東麗股份有限公司製“Lumirror"(註冊商標)X10S(125μm))。 A hydrolysis-resistant biaxially stretched PET film ("Lumirror" (registered trademark) X10S (125 μm) manufactured by Toray Industries, Inc.) was prepared as a plastic film.
藉由乾式積層機(岡崎機械工業股份有限公司製附單色印刷的乾式積層機OG/DL-130TA-AF)，在上述“Lumirror"X10S塗布異氰酸酯交聯型黏著劑(大日本油墨化學工業股份有限公司製，LX-903/KL-75=8/1)，固體成分塗布厚度為5μm，並使其乾燥，以60N/cm的夾持壓與前述聚烯烴系樹脂薄膜的B層側實施積層。 The above-mentioned "Lumirror" X10S coated isocyanate cross-linking adhesive (Daily Ink Chemical Industry Co., Ltd.) by a dry laminator (Okasaki Machinery Co., Ltd., a monochrome laminator OG/DL-130TA-AF) Co., Ltd., LX-903/KL-75=8/1), a solid component coating thickness of 5 μm, and drying, and a layering of the B-layer side of the polyolefin-based resin film at a clamping pressure of 60 N/cm. .
在溫度40℃下使積層薄膜熟成72小時，促進黏著劑層的硬化反應，而製成太陽能電池模組用背面保護片。將其評估結果揭示於表2。 The laminated film was aged at a temperature of 40 ° C for 72 hours to promote the hardening reaction of the adhesive layer, and a back protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期為60N/cm以上，耐濕熱性試驗48小時後也在40N/cm以上。 The adhesion strength between the protective sheet and the EVA sheet was 60 N/cm or more at the initial stage, and was 40 N/cm or more after 48 hours of the moist heat resistance test.
(實施例9) (Example 9)
A層所使用的樹脂採用相對於r-EPBC80重量%混合HDPE20重量%而成的樹脂。(a)/(b)的重量組成比為0.25。B層所使用的樹脂採用相對於h-PP80重量%混合氧化鈦MB20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。 The resin used for the layer A was a resin obtained by mixing 20% by weight of HDPE with respect to 80% by weight of r-EPBC. The weight composition ratio of (a)/(b) is 0.25. The resin used for the layer B was a resin obtained by mixing 20% by weight of titanium oxide MB with 80% by weight of h-PP. The amount of titanium oxide added to the whitening agent was 12% by weight.
將以這種方式準備的A層、B層各層的各個樹脂供給至單軸熔融擠出機，分別在260℃下使其熔融，導引至A層/B層型的多流道型T模具，擠出至保持在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風使其冷卻固化，而得到各層厚度構成比率為A層/B層=10%/90%的厚度150μm的聚烯烴系樹脂薄膜，除此之外，以與實施例8同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 Each resin of each of the A layer and the B layer prepared in this manner was supplied to a uniaxial melt extruder, and melted at 260 ° C, respectively, and guided to a multi-channel type T mold of the A layer/B layer type. Extrusion to a casting drum maintained at 30 ° C, blowing cold air of 25 ° C from the non-roller side to cool and solidify, and obtaining a thickness ratio of each layer of A layer / B layer = 10% / 90% 150 μm A back surface protective sheet for a solar cell module was produced in the same manner as in Example 8 except that the polyolefin resin film was used. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期為60N/cm以上，耐濕熱性試驗48小時後也在40N/cm以上。 The adhesion strength between the protective sheet and the EVA sheet was 60 N/cm or more at the initial stage, and was 40 N/cm or more after 48 hours of the moist heat resistance test.
(實施例10) (Embodiment 10)
A層所使用的樹脂採用相對於r-EPBC80重量%混合LLDPE(C6)20重量%而成的樹脂。(a)/(b)的重量組成比為0.25。B層所使用的樹脂採用相對於r-EPC(1)80重量%混合氧化鈦MB20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。 The resin used for the layer A was a resin obtained by mixing 20% by weight of LLDPE (C6) with respect to 80% by weight of r-EPBC. The weight composition ratio of (a)/(b) is 0.25. The resin used for the layer B was a resin obtained by mixing 80% by weight of titanium oxide MB with 80% by weight of r-EPC (1). The amount of titanium oxide added to the whitening agent was 12% by weight.
將以這種方式準備的A層、B層各層的各個樹脂供給至單軸熔融擠出機，分別在260℃下使其熔融，導引至A層/B層多流道型T模具，擠出至保持在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風使其冷卻固化，而得到各層厚度構成比率為A層/B層=20%/80%且厚度為150μm的聚烯烴系樹脂薄膜。 Each resin of each of the A layer and the B layer prepared in this manner was supplied to a uniaxial melt extruder, and melted at 260 ° C, respectively, and guided to an A layer / B layer multi-flow type T mold, and extruded. It was discharged to a casting drum maintained at 30 ° C, and cold air of 25 ° C was blown from the non-roller surface side to be solidified by cooling, thereby obtaining a polymer having a thickness ratio of each layer of layer A/B layer=20%/80% and thickness of 150 μm. An olefin resin film.
對於此聚烯烴系樹脂薄膜的兩面在大氣中以23W．min/m2的電能量實施電暈放電處理，分別使A層、及B層表面的潤濕張力成為40mN/m，並且加以捲繞，除此之外，以與實施例8同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 For both sides of this polyolefin-based resin film, it is 23 W in the atmosphere. The electric energy of min/m 2 was subjected to a corona discharge treatment, and the wetting tension of the surface of the layer A and the layer B was 40 mN/m, and wound, and the same manner as in the example 8 was carried out. A back protective sheet for the solar cell module. The results of the evaluation are disclosed in Table 2.
本聚烯烴系樹脂薄膜由於A層、及B層的兩面經過表面改質處理，因此雖然薄膜彼此的潤滑性稍差，但仍在可使用的範圍，作為太陽能電池模組用背面保護片也沒有問題。 In the polyolefin-based resin film, since both surfaces of the A layer and the B layer are subjected to surface modification treatment, although the lubricity of the films is slightly inferior, it is still usable, and there is no back protective sheet for a solar cell module. problem.
(實施例11) (Example 11)
A層所使用的樹脂採用相對於r-EPBC75重量%混合LLDPE(C4)10重量%、HDPE15重量%而成的樹脂。此時，(a)/(b)的重量組成比為0.33。B層所使用的樹脂採用相對於r-EPC(1)80重量%混合氧化鈦MB20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。C層所使用的樹脂採用b-PP100重量%。 The resin used for the layer A was a resin obtained by mixing 10 wt% of LLDPE (C4) and 15 wt% of HDPE with respect to 75 wt% of r-EPBC. At this time, the weight composition ratio of (a)/(b) was 0.33. The resin used for the layer B was a resin obtained by mixing 80% by weight of titanium oxide MB with 80% by weight of r-EPC (1). The amount of titanium oxide added to the whitening agent was 12% by weight. The resin used for the layer C was 100% by weight of b-PP.
將以這種方式準備的A層、B層、C層各層各個樹脂供給至單軸熔融擠出機，分別在260℃下使其熔融，導引至A層/B層/C層型的多流道型T模具，擠出至保持在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風，並使其冷卻固化，而得到各層厚度構成比率為A層/B層/C層=20%/70%/10%的厚度150μm的聚烯烴系樹脂薄膜。以與實施例8同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 Each of the layers A, B, and C prepared in this manner was supplied to a uniaxial melt extruder, and melted at 260 ° C, respectively, and guided to the A layer / B layer / C layer type. The flow path type T mold was extruded to a casting drum maintained at 30 ° C, and cold air of 25 ° C was blown from the non-roller surface side, and cooled and solidified, thereby obtaining a thickness ratio of each layer to A layer / B layer / C layer. = 20% / 70% / 10% of a polyolefin resin film having a thickness of 150 μm. A back protective sheet for a solar cell module was produced in the same manner as in Example 8. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期為60N/cm以上，耐濕熱性試驗48小時後也在40N/cm以上。 The adhesion strength between the protective sheet and the EVA sheet was 60 N/cm or more at the initial stage, and was 40 N/cm or more after 48 hours of the moist heat resistance test.
(實施例12) (Embodiment 12)
A層所使用的樹脂採用相對於r-EPC(2)(熔點135℃)65重量%混合LLDPE(C4)35重量%而成的樹脂。(a)/(b)的重量組成比為0.54。B層所使用的樹脂採用相對於r-EPC(1)80重量%混合氧化鈦MB20重量%而成的樹脂。白化劑的氧化鈦的添加量為12重量%。C層所使用的樹脂採用b-PP100重量%。 The resin used for the layer A was a resin obtained by mixing 35 wt% of LLDPE (C4) with respect to r-EPC (2) (melting point: 135 ° C). The weight composition ratio of (a)/(b) was 0.54. The resin used for the layer B was a resin obtained by mixing 80% by weight of titanium oxide MB with 80% by weight of r-EPC (1). The amount of titanium oxide added to the whitening agent was 12% by weight. The resin used for the layer C was 100% by weight of b-PP.
將以這種方式準備的A層、B層及C層各層的各個樹脂供給至單軸熔融擠出機，分別在260℃下使其熔融， 導引至A層/B層/C層型的多流道型的T模具，擠出至保持在30℃的澆鑄滾筒上，由非滾筒面側吹送25℃的冷風使其冷卻固化，而得到各層厚度構成比率為A層/B層/C層=20%/70%/10%的厚度150μm的聚烯烴系樹脂薄膜。對於此聚烯烴系樹脂薄膜的C層側在大氣中以23W．min/m2的電能量實施電暈放電處理，使C層表面的潤濕張力成為40mN/m，並且加以捲繞。以與實施例8同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 Each of the resins of the layers A, B, and C prepared in this manner was supplied to a uniaxial melt extruder, and melted at 260 ° C, respectively, and guided to the A layer / B layer / C layer type. The multi-flow type T-die was extruded to a casting drum maintained at 30 ° C, and cold air of 25 ° C was blown from the non-roller surface side to be cooled and solidified, and the thickness ratio of each layer was A layer / B layer / C layer. = 20% / 70% / 10% of a polyolefin resin film having a thickness of 150 μm. The C layer side of this polyolefin-based resin film is 23 W in the atmosphere. The electric energy of min/m 2 was subjected to corona discharge treatment so that the wetting tension of the surface of the layer C became 40 mN/m, and was wound. A back protective sheet for a solar cell module was produced in the same manner as in Example 8. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期為60N/cm以上，耐濕熱性試驗48小時後也在40N/cm以上。 The adhesion strength between the protective sheet and the EVA sheet was 60 N/cm or more at the initial stage, and was 40 N/cm or more after 48 hours of the moist heat resistance test.
(實施例13) (Example 13)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用相對於r-EPC(2)60重量%混合LLDPE(C4)40重量%而成的樹脂，製作出((a)/(b)的重量組成比0.67)聚烯烴樹脂系薄膜。以與實施例8同樣的方法製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In the example 12, the resin used for the layer A of the polyolefin resin film is a resin obtained by mixing 40% by weight of LLDPE (C4) with respect to 60% by weight of r-EPC (2), and (a) / (b) A weight ratio of 0.67) polyolefin resin-based film. A back protective sheet for a solar cell module was produced in the same manner as in Example 8. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期雖然低於60N/cm，然而耐濕熱性試驗48小時後為40N/cm以上。 Although the adhesion strength between the protective sheet and the EVA sheet was less than 60 N/cm at the initial stage, the heat resistance test was 40 N/cm or more after 48 hours.
(實施例14) (Example 14)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用相對於r-EPC(2)90重量%混合LLDPE(C4)10重量%而成的樹脂，製作出((a)/(b)的重量組成比0.11)聚烯烴系樹脂薄膜，並製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In the example 12, the resin used for the layer A of the polyolefin resin film is a resin obtained by mixing 10% by weight of LLDPE (C4) with 90% by weight of r-EPC (2), and (a) / (b) A polyolefin resin film having a weight composition ratio of 0.11), and a back surface protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期為60N/cm以上，耐濕熱性試驗48小時後也在40N/cm以上。由於A層的聚乙烯系樹脂的比率低，因此雖然潤滑性稍差，但是仍在實用的等級。 The adhesion strength between the protective sheet and the EVA sheet was 60 N/cm or more at the initial stage, and was 40 N/cm or more after 48 hours of the moist heat resistance test. Since the ratio of the polyethylene-based resin of the A layer is low, although the lubricity is slightly inferior, it is still in a practical grade.
(實施例15) (Example 15)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用相對於r-EPC(2)50重量%混合LLDPE(C4)50重量%而成的樹脂，製作出((a)/(b)的重量組成比1.0)聚烯烴系樹脂薄膜，製作出太陽能電池模組用背面保護片。將其評估結果揭示於表1。 In the example 12, the resin used for the layer A of the polyolefin resin film was prepared by mixing 50% by weight of LLDPE (C4) with 50% by weight of r-EPC (2), and (a) / (b) The weight composition ratio of 1.0) The polyolefin resin film was used to produce a back surface protective sheet for a solar cell module. The results of the evaluation are disclosed in Table 1.
本保護片與EVA片的密著強度在初期雖然低於60N/cm，然而在耐濕熱性試驗48小時後為40N/cm以上。但是，耐濕熱性試驗96小時後低於40N/cm。 Although the adhesion strength between the protective sheet and the EVA sheet was less than 60 N/cm at the initial stage, it was 40 N/cm or more after 48 hours of the moist heat resistance test. However, the heat and humidity resistance test was lower than 40 N/cm after 96 hours.
(比較例5) (Comparative Example 5)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用LLDPE(C4)100重量%，製作出聚烯烴系樹脂薄膜，並製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In the example 12, the resin used for the layer A of the polyolefin-based resin film was 100% by weight of LLDPE (C4) to prepare a polyolefin-based resin film, and a back surface protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期未滿60N/cm、耐濕熱性試驗48小時後也未滿40N/cm而並不充足。EVA片與A層雖然密著，然而A層與B層間的密著強度不足，因此並未發揮出所希望的密著強度。 The adhesion strength between the protective sheet and the EVA sheet was less than 60 N/cm at the initial stage and less than 40 N/cm after 48 hours of the heat and humidity resistance test, which was not sufficient. Although the EVA sheet and the A layer are closely adhered to each other, the adhesion strength between the A layer and the B layer is insufficient, so that the desired adhesion strength is not exhibited.
(比較例6) (Comparative Example 6)
在實施例8之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用r-EPBC100重量%，製作出聚烯烴系樹脂薄 膜，並製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In the eighth embodiment, the resin used for the layer A of the polyolefin-based resin film was made of r-EPBC 100% by weight to prepare a polyolefin-based resin. The film and the back protective sheet for the solar cell module are produced. The results of the evaluation are disclosed in Table 2.
本聚烯烴系樹脂薄膜，在動摩擦係數高，製成卷物時會觀察到黏連，在作為太陽能電池模組用背面保護片時，與EVA片的密著強度沒有問題，然而加工性有問題。 The polyolefin-based resin film has a high coefficient of dynamic friction and is observed to be adhered when the roll is formed. When used as a back protective sheet for a solar cell module, there is no problem in adhesion strength to the EVA sheet, but there is a problem in workability. .
(比較例7) (Comparative Example 7)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用混合LLDPE(C4)30重量%、h-PP(熔點160℃)70重量%而成的樹脂((a)/(b)的重量組成比0.43)，製作出聚烯烴系樹脂薄膜，並製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In the example 12, the resin used for the layer A of the polyolefin resin film is a resin obtained by mixing 30% by weight of LLDPE (C4) and 70% by weight of h-PP (melting point: 160 ° C) ((a)/( b) The weight composition ratio of 0.43) was prepared to produce a polyolefin resin film, and a back surface protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期未滿60N/cm，耐濕熱性試驗後也未滿40N/cm而並不充足。 The adhesion strength between the protective sheet and the EVA sheet was less than 60 N/cm at the initial stage, and was not sufficient at 40 N/cm after the heat and humidity resistance test.
(比較例8) (Comparative Example 8)
在實施例12之中，聚烯烴系樹脂薄膜的A層所使用的樹脂採用LLDPE(C4)35重量%、r-EPC(2)(熔點147℃)65重量%((a)/(b)的重量組成比0.54)，製作出聚烯烴系樹脂薄膜，並製作出太陽能電池模組用背面保護片。將其評估結果揭示於表2。 In Example 12, the resin used for the layer A of the polyolefin-based resin film was 35 wt% of LLDPE (C4) and 65 wt% of r-EPC (2) (melting point 147 ° C) ((a)/(b). A weight ratio of 0.54) was used to prepare a polyolefin resin film, and a back surface protective sheet for a solar cell module was produced. The results of the evaluation are disclosed in Table 2.
本保護片與EVA片的密著強度在初期未滿60N/cm，耐濕熱性試驗後也未滿40N/cm而並不充足。 The adhesion strength between the protective sheet and the EVA sheet was less than 60 N/cm at the initial stage, and was not sufficient at 40 N/cm after the heat and humidity resistance test.
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| JP7067154B2 (en) * | 2018-03-14 | 2022-05-16 | 大日本印刷株式会社 | Backside protective sheet for solar cell module and solar cell module with integrated building materials |
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| WO2012043248A1 (en) * | 2010-09-29 | 2012-04-05 | 東レフィルム加工株式会社 | Multilayered polyolefin resin film for back protection sheet for solar cell |
| JP5989427B2 (en) * | 2011-07-07 | 2016-09-07 | 株式会社ユポ・コーポレーション | Solar cell backsheet and solar cell using the same |
| WO2013024892A1 (en) * | 2011-08-17 | 2013-02-21 | 富士フイルム株式会社 | Solar cell back sheet, method for manufacturing same, and solar cell module |
| WO2013039234A1 (en) * | 2011-09-16 | 2013-03-21 | 三菱樹脂株式会社 | Solar cell protective material |
| JP5974294B2 (en) * | 2011-10-31 | 2016-08-23 | 東洋インキＳｃホールディングス株式会社 | Easy adhesive for solar cell back surface protective sheet, solar cell back surface protective sheet, and solar cell module |
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