TW201547034A - Anti-PID film for solar cell and anti-PID solar cell module using the same - Google Patents
Anti-PID film for solar cell and anti-PID solar cell module using the same Download PDFInfo
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- TW201547034A TW201547034A TW104105848A TW104105848A TW201547034A TW 201547034 A TW201547034 A TW 201547034A TW 104105848 A TW104105848 A TW 104105848A TW 104105848 A TW104105848 A TW 104105848A TW 201547034 A TW201547034 A TW 201547034A
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- Taiwan
- Prior art keywords
- film
- solar cell
- pid
- cell module
- cyclic olefin
- Prior art date
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- 125000004122 cyclic group Chemical group 0.000 claims abstract description 30
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
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- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
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- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於一種對太陽電池模組中之太陽電池元件防止自覆蓋玻璃所釋放之鹼金屬所致之劣化的PID 對策膜及使用該膜之太陽電池模組。The present invention relates to a PID countermeasure film for preventing deterioration of a solar cell element in a solar cell module from alkali metal released from a cover glass, and a solar cell module using the same.
作為太陽電池模組之代表性構成， 已知有所謂覆板( supe r s t ra t e ) 構造， 即， 利用一對接著膜自兩面側夾著太陽電池元件， 進而於太陽光受光側之接著膜固定玻璃等透明基材， 且於背面側之接著膜固定保護材(背部片材)。或者， 有利用覆蓋玻璃夾著模組之兩面之所謂玻璃/玻璃構造之模組。有為了提高模組轉換效率而應用兩面發電單元之情形。於此種構成中， 對於接著膜或發電元件保護膜， 要求接著性、耐候性等各特性， 尤其是太陽光之受光側要求較高之透明性， 滿足該等要求之接著膜例如於專利文獻1～ 專利文獻3 等中為公知。As a typical configuration of the solar battery module, a so-called supper rst structure has been known, that is, a solar cell element is sandwiched between the both sides by a pair of adhesive films, and the film is fixed on the solar light receiving side. A transparent substrate such as glass is used, and a protective material (back sheet) is attached to the film on the back side. Alternatively, there is a so-called glass/glass construction module that covers the two sides of the module with a cover glass. There are cases where a two-sided power generation unit is applied in order to improve module conversion efficiency. In such a configuration, the adhesive film or the power-generating element protective film is required to have various properties such as adhesion and weather resistance, and in particular, transparency is required on the light-receiving side of sunlight, and the adhesive film satisfying such requirements is, for example, a patent document. 1 to Patent Document 3 and the like are known.
除該等特性以外，需要對因產生系統發電量於半年至數年間降低數十百分比之所謂PID(Potential Induced degradation，電勢誘發衰減)現象所引起之發電劣化作出對策。於專利文獻1中，介紹了於電池單元與覆蓋玻璃之間積層由氟系膜等所構成之高絕緣膜的技術。另外，於專利文獻2中，介紹了為減輕自玻璃釋放之鹼金屬之影響而利用矽烷偶合劑對玻璃表面進行表面處理的技術。又，於專利文獻3中，揭示有一種太陽電池模組，其具有包含環狀烯烴系樹脂之層、及包含乙烯-乙酸乙烯酯共聚物之層，且至少1層之上述包含乙烯-乙酸乙烯酯共聚物之層係以上述包含環狀烯烴系樹脂之層為基準而配置於遠離太陽電池單元之側。In addition to these characteristics, it is necessary to take measures against the deterioration of power generation caused by the phenomenon of the so-called PID (Potential Induced degradation) phenomenon in which the system power generation amount is reduced by several tens of percent in half a year to several years. Patent Document 1 discloses a technique of laminating a high insulating film made of a fluorine-based film or the like between a battery cell and a cover glass. Further, Patent Document 2 discloses a technique of surface-treating a glass surface with a decane coupling agent to reduce the influence of alkali metal released from the glass. Further, Patent Document 3 discloses a solar battery module having a layer containing a cyclic olefin resin and a layer containing an ethylene-vinyl acetate copolymer, and at least one of the above-mentioned ethylene-vinyl acetate is contained. The layer of the ester copolymer is disposed on the side away from the solar cell unit based on the layer containing the cyclic olefin resin described above.
然而，於不明確PID現象產生機制之情況下，於獨自設計之PID試驗方法中觀察到發電劣化率之降低。關於驗證試驗，雖然保證20年效果之條件為85℃、85RH(相對溼度)%、1000小時，而假定在暴露於高電壓下之發電站使用時之條件為至少1000小時，但該等試驗為100小時，並非原本目的之試驗。迄今為止尚無發明揭示有於與實地且20年來對應之實驗室試驗條件下是否產生發電劣化之結果。However, in the case where the PID phenomenon generation mechanism is not clarified, a decrease in the power generation deterioration rate is observed in the PID test method designed by itself. Regarding the verification test, although the conditions for ensuring the 20-year effect are 85 ° C, 85 RH (relative humidity) %, 1000 hours, and the conditions for use in a power station exposed to a high voltage are assumed to be at least 1000 hours, the tests are 100 hours, not the original purpose of the test. To date, no invention has revealed whether or not power generation degradation occurs under laboratory test conditions corresponding to the field and for 20 years.
發明者根據產生PID現象之模組的破壞分析結果，對PID現象之產生機制進行努力研究，證明有以下的結果。於實地藉由產生PID現象之模組的破壞分析而明確指出於廣泛使用之P型矽半導體中，若鈉離子堆積而覆蓋白板玻璃側之矽單元之總表面積之15%左右，則形成金屬鈉層，pn構造之n層P化，其結果為，喪失量子力學上藉由pn接合所發現之半導體之性質，無法發揮出光電效應而變得無法發電。又，已知發電劣化除由作為矽單元之半導體之劣化引起以外，亦由表面電極及內部連接線之電子集電能力之降低而引起。已知所謂集電能力之降低係由如下情況引起，即，因EVA(Ethylene Vinyl Acetate Copolymer，乙烯/乙酸乙烯酯共聚物)密封材發生劣化而釋放之乙酸將焊料成分溶解，又，作為表面電極與電池單元之接著劑進行添加而將某玻璃成分溶解。已知運行21年之日本國內太陽電池模組下部之角部(角部矽單元的模組角部側之邊緣部的受光面側)之乙酸量為120 μg/g。已知於實驗室中，於20 cm見方之相同構造之模組中，使用三井化學公司製造之EVA的單元邊緣部之乙酸量於85℃、85RH%之溫濕試驗中對應於2500小時。The inventors conducted an effort to study the mechanism of the PID phenomenon based on the damage analysis result of the module generating the PID phenomenon, and proved the following results. In the field, the damage analysis of the module that generates the PID phenomenon clearly indicates that in the widely used P-type germanium semiconductor, if sodium ions are deposited to cover about 15% of the total surface area of the germanium unit on the white glass side, metal sodium is formed. In the layer, the n-layer of the pn structure is P-formed. As a result, the nature of the semiconductor discovered by pn bonding in quantum mechanics is lost, and the photoelectric effect cannot be exhibited, and power generation cannot be achieved. Further, it is known that power generation deterioration is caused not only by deterioration of a semiconductor which is a germanium unit but also by a decrease in electron collecting ability of the surface electrode and the internal connection line. It is known that the reduction in the current collecting ability is caused by the fact that acetic acid released by the deterioration of EVA (Ethylene Vinyl Acetate Copolymer) sealing material dissolves the solder component and, as a surface electrode, Adding to the adhesive of the battery unit dissolves a certain glass component. It is known that the amount of acetic acid in the corner portion of the lower portion of the solar cell module in Japan for 21 years (the light receiving surface side of the edge portion of the corner portion of the corner portion unit) is 120 μg/g. It is known that in the laboratory of the same structure of 20 cm square, the amount of acetic acid in the edge portion of the unit using EVA manufactured by Mitsui Chemicals Co., Ltd. corresponds to 2500 hours in the temperature and humidity test at 85 ° C and 85 RH %.
由此，可知PID試驗條件並非以現今標準化如60℃、85RH%、96小時、-1000 V之條件進行研究，而是於溫濕試驗中於85%、85RH%、2500小時之條件下施加-1000 V之條件，其係相當於20年之試驗條件。Therefore, it can be seen that the PID test conditions are not studied under the conditions of current standardization such as 60 ° C, 85 RH %, 96 hours, -1000 V, but are applied in the temperature and humidity test at 85%, 85 RH%, 2500 hours - The condition of 1000 V is equivalent to 20 years of test conditions.
專利文獻3所記載之太陽電池模組用之保護膜係使用環狀烯烴系樹脂，其玻璃轉移溫度為較寬之範圍，為80℃～250℃，又，膜之厚度亦為較寬之範圍，為5 μm～200 μm。於該公開公報所記載之範圍內，作為膜之成形性較差，又，即便能夠成形亦大多產生裂痕，無法供於實用。又，太陽電池模組有大型化之傾向，其尺寸達到2 m×4 m(縱×橫)以上之大小。專利文獻3所記載之太陽電池模組用之保護膜無法成形為此種尺寸之太陽電池模組用之膜。 [先前技術文獻] [專利文獻]The protective film for a solar cell module described in Patent Document 3 is a cyclic olefin-based resin having a glass transition temperature in a wide range of 80 ° C to 250 ° C, and the thickness of the film is also a wide range. , from 5 μm to 200 μm. In the range described in the publication, the formability of the film is inferior, and even if it can be formed, cracks are often generated and it is not practical. Further, the solar cell module has a tendency to increase in size, and its size is 2 m × 4 m (vertical × horizontal) or more. The protective film for a solar cell module described in Patent Document 3 cannot be formed into a film for a solar cell module of such a size. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特表2013-502051 [專利文獻2]日本專利特開2008-273783 [專利文獻3]日本專利特開2006-198922[Patent Document 1] Japanese Patent Laid-Open No. 2013-502051 [Patent Document 2] Japanese Patent Laid-Open No. 2008-273783 [Patent Document 3] Japanese Patent Laid-Open No. 2006-198922
[發明所欲解決之問題][The problem that the invention wants to solve]
本發明之目的在於提供一種解決上述問題的太陽電池用PID對策膜及使用該對策膜之PID對策太陽電池模組，該太陽電池用PID對策膜對於自太陽電池模組之覆蓋玻璃所釋放之鹼金屬離子之阻隔性優異，且耐熱性、耐光性優異。 [解決問題之技術手段]An object of the present invention is to provide a PID countermeasure film for a solar cell that solves the above problems, and a PID countermeasure solar cell module using the same, which is a base for releasing a base from a cover glass of a solar cell module. Metal ions have excellent barrier properties and are excellent in heat resistance and light resistance. [Technical means to solve the problem]
＜1＞第1發明 用以解決上述問題之第1發明的PID對策膜的特徵在於：其係於太陽電池模組內之太陽電池發電元件與覆蓋玻璃之中間積層而成，並且係寬度為80 cm以上且玻璃轉移溫度為75℃以上、95℃以下之環狀烯烴系樹脂膜，且膜厚度為40 μm以上、200 μm以下。<1> The PID countermeasure film according to the first aspect of the invention of the first aspect of the invention is characterized in that it is formed by laminating a solar cell power generation element and a cover glass in a solar cell module, and has a width of 80. A cyclic olefin-based resin film having a glass transition temperature of not less than 0.05 cm and not more than 95 ° C and a film thickness of 40 μm or more and 200 μm or less.
本發明之環狀烯烴系樹脂膜(以下，簡稱為「PID對策膜」)係設置於太陽電池模組內之太陽電池發電元件與覆蓋玻璃之中間。本發明之PID對策膜之玻璃轉移溫度為75℃以上、95℃以下，較佳為80℃以上、90℃以下。若玻璃轉移溫度未達75℃，則因太陽電池之交聯反應步驟即層壓步驟之成型熱而導致膜發生部分流動化，於模組之受光面側形成包含圓形褶皺之痘痕，因此欠佳。若超過95℃，則於將膜捲繞成輥狀時，會自側面部發生破裂，而無法將膜捲取。進而，於太陽電池模組成型後，經過一週左右之後，於太陽電池模組內產生無數微裂縫，外觀不良，故而欠佳。The cyclic olefin resin film of the present invention (hereinafter, simply referred to as "PID countermeasure film") is provided between the solar cell power generation element and the cover glass in the solar cell module. The glass transition temperature of the PID countermeasure film of the present invention is 75 ° C or more and 95 ° C or less, preferably 80 ° C or more and 90 ° C or less. If the glass transition temperature is less than 75 ° C, the film is partially fluidized due to the heat of the lamination reaction step of the solar cell, that is, the molding step of the lamination step, and the pock marks containing the circular wrinkles are formed on the light-receiving side of the module, so good. When it exceeds 95 ° C, when the film is wound into a roll shape, cracking occurs from the side surface portion, and the film cannot be taken up. Further, after the solar cell module is molded, after a week or so, numerous micro cracks are generated in the solar cell module, and the appearance is poor, which is not preferable.
又，本發明之PID對策膜之厚度為40 μm以上、200 μm以下，較佳為60 μm以上、100 μm以下，進而較佳為70 μ以上、90 μ以下。若膜厚度小於40 μm，則膜強度明顯降低，有因膜之捲取步驟中所施加之張力而發生斷裂之情況，因此欠佳。又，若厚度超過200 μm，則會於膜捲之接近支管直徑之部分發生破裂，因此欠佳。又，若使用厚度超過200 μm之較厚之膜，則將膜成形後24小時後，於太陽電池模組成型體之受光面側產生無數微裂縫，製品外觀不良，因此欠佳。Further, the thickness of the PID countermeasure film of the present invention is 40 μm or more and 200 μm or less, preferably 60 μm or more and 100 μm or less, and more preferably 70 μm or more and 90 μm or less. If the film thickness is less than 40 μm, the film strength is remarkably lowered, and the film is broken due to the tension applied in the winding step of the film, which is not preferable. Further, if the thickness exceeds 200 μm, cracking occurs in the portion of the film roll close to the diameter of the branch pipe, which is not preferable. Further, when a thick film having a thickness of more than 200 μm is used, after 24 hours from the film formation, numerous micro cracks are generated on the light-receiving surface side of the solar cell module molded body, and the appearance of the product is poor, which is not preferable.
又，關於本發明之PID對策膜，可製造出能夠用於尺寸大型化至2 m×4 m(縱×橫)以上之太陽電池模組的尺寸(寬度80 cm以上)者。如此，即便為大尺寸之PID對策膜，亦可在完全無破裂等之情況下提供。又，此種大尺寸之PID對策膜藉由先前技術未能實現。Further, in the PID countermeasure film of the present invention, it is possible to manufacture a size (width 80 cm or more) of a solar battery module that can be used to increase in size to 2 m × 4 m (length × width) or more. In this way, even a large-sized PID countermeasure film can be provided without any breakage or the like. Moreover, such a large-sized PID countermeasure film has not been realized by the prior art.
本發明之PID對策膜防止自太陽電池模組之覆蓋玻璃所釋放之鈉離子或鉀離子移動至太陽電池模組內之發電元件(結晶系單元(cell)、太陽電池單元等)之表面，因此可完全地防止大規模太陽能發電站(Mega Solar)中頻繁產生之因PID所致之發電劣化。又，關於本發明之PID對策，作為太陽電池模組用接著膜而要求之耐候性、耐熱性、透明性、防水性、防濕性優異。因此，可實現太陽電池模組之長壽命化。進而，可提供於太陽電池模組內之太陽電池單元與覆蓋玻璃之間之密封部分完全無破裂等的外觀良好之太陽電池模組。The PID countermeasure film of the present invention prevents sodium ions or potassium ions released from the cover glass of the solar cell module from moving to the surface of the power generation element (crystal cell, solar cell, etc.) in the solar cell module, It is possible to completely prevent the deterioration of power generation due to PID which is frequently generated in a large-scale solar power station (Mega Solar). In addition, the PID measures of the present invention are excellent in weather resistance, heat resistance, transparency, water repellency, and moisture resistance required as a film for a solar cell module. Therefore, the long life of the solar cell module can be achieved. Further, it is possible to provide a solar cell module having a good appearance such that the sealed portion between the solar cell unit and the cover glass in the solar cell module is completely free from cracks.
本發明之PID對策膜有容易破裂之傾向，可於貼附有如聚乙烯原材料之兼具伸縮性與強度之保護膜之狀態下進行膜捲取。或者，亦可使用氧化矽等微粒子之粉末而防止膜輥之捲取皺褶。The PID countermeasure film of the present invention tends to be easily broken, and the film can be taken up in a state in which a protective film having both flexibility and strength such as a polyethylene material is attached. Alternatively, a powder of fine particles such as cerium oxide may be used to prevent wrinkling of the film roll.
＜2＞第2發明 第2發明之PID對策膜係如第1發明，其特徵在於：環狀烯烴系樹脂為乙烯及/或a-烯烴與環狀烯烴之共聚物。<2> The second aspect of the invention relates to a PID countermeasure film according to the first aspect of the invention, characterized in that the cyclic olefin resin is a copolymer of ethylene and/or an a-olefin and a cyclic olefin.
第2發明係環狀烯烴系樹脂為乙烯及/或a-烯烴與環狀烯烴之共聚物的PID對策膜，乙烯及/或a-烯烴中，最佳為單獨使用乙烯。According to a second aspect of the invention, the cyclic olefin resin is a PID countermeasure film of a copolymer of ethylene and/or an a-olefin and a cyclic olefin. Among ethylene and/or a-olefin, ethylene is preferably used alone.
根據第2發明，環狀烯烴系樹脂為乙烯及/或a-烯烴與環狀烯烴之共聚物。藉由使用環狀烯烴系共聚物，除了更可能提高PID對策片之耐候性且完全防止PID之效果以外，亦發現膜壽命提高之效果。因此，使用該膜之太陽電池模組之壽命進一步提高。According to the second aspect of the invention, the cyclic olefin resin is a copolymer of ethylene and/or an a-olefin and a cyclic olefin. By using a cyclic olefin-based copolymer, in addition to the fact that the weather resistance of the PID countermeasure sheet is more likely to be improved and the effect of PID is completely prevented, the effect of improving the film life is also found. Therefore, the life of the solar cell module using the film is further improved.
＜3＞第3發明 第3發明之PID對策膜，其特徵在於如第1發明或第2發明所述的PID對策膜與密封用膜成為一體。(3) The PID countermeasure film according to the third aspect of the invention is characterized in that the PID countermeasure film according to the first invention or the second invention is integrated with the film for sealing.
第3發明之PID對策膜係與密封用膜一體化。作為該密封用膜，可設為EVA樹脂膜、PVB(polyvinyl butyral，聚乙烯丁醛)樹脂膜、離子聚合物膜等太陽電池模組所使用之密封用膜。The PID countermeasure film system according to the third aspect of the invention is integrated with the film for sealing. The film for sealing can be a film for sealing used in a solar cell module such as an EVA resin film, a PVB (polyvinyl butyral) resin film, or an ion polymer film.
根據第3發明，PID對策膜係與密封膜一體化，因此於製造太陽電池模組之步驟中，可簡化對太陽電池單元積層各構件之步驟。According to the third aspect of the invention, since the PID countermeasure film system is integrated with the sealing film, the step of laminating each member of the solar battery cell can be simplified in the step of manufacturing the solar battery module.
＜4＞第4發明 第4發明之太陽電池模組，其特徵在於如第1發明至第3發明中之任一者所述的PID對策膜係設置於EVA密封膜與覆蓋玻璃之間。(4) The solar cell module according to any one of the first to third aspects of the present invention, wherein the PID countermeasure film is provided between the EVA sealing film and the cover glass.
本發明之太陽電池太陽電池模組係為於覆蓋玻璃與現有太陽電池用密封膜之間設置有第1發明至第3發明之PID對策膜的構成。使用本發明之PID對策膜之太陽電池模組係以覆蓋玻璃、現有密封膜、本發明之膜、現有密封膜、太陽電池單元、現有密封膜、背面材之順序將該等構件積層。積層後，藉由以130℃以上之熱進行壓製成型而將各自界面接著，藉此成為PID對策用之太陽電池模組。作為現有密封膜，通常較佳為使用EVA密封材。覆蓋玻璃可為釋放鈉離子之白板玻璃，亦可為玻璃表面經鉀離子置換之化學強化玻璃。化學強化玻璃由於強度較高，故而可實現薄壁化，並可容易地製造輕量化太陽電池模組。The solar cell solar cell module of the present invention has a configuration in which the PID countermeasure film of the first to third inventions is provided between the cover glass and the conventional solar cell sealing film. The solar cell module using the PID countermeasure film of the present invention is laminated with a cover glass, a conventional sealing film, a film of the present invention, a conventional sealing film, a solar cell unit, a conventional sealing film, and a back material. After lamination, the respective interfaces are bonded by press molding at a temperature of 130 ° C or higher, thereby becoming a solar cell module for PID countermeasures. As the conventional sealing film, it is generally preferred to use an EVA sealing material. The cover glass may be a white glass that releases sodium ions, or a chemically strengthened glass whose surface is replaced by potassium ions. Since the chemically strengthened glass has high strength, it can be made thinner, and a lightweight solar cell module can be easily manufactured.
藉由本發明之構成所獲得之該太陽電池模組完全不產生PID，作為製品之防水性提高，又，可持續超長時間地確保耐候性，可實現太陽電池模組之長壽命化。The solar cell module obtained by the constitution of the present invention does not generate PID at all, and the waterproof property of the product is improved, and the weather resistance is ensured for a long time, and the life of the solar cell module can be extended.
＜5＞第5發明 第5發明之太陽電池模組之特徵在於：第1發明至第3發明中之任一種PID對策膜覆蓋結晶系單元面積之至少85%以上。(5) The solar battery module according to the fifth aspect of the invention is characterized in that, in any one of the first to third inventions, the PID countermeasure film covers at least 85% of the area of the crystal unit.
如上所述，本發明之膜只要至少於太陽電池單元之上部積層即可，而且只要覆蓋結晶系單元面積之至少85%以上即可。若本發明之PID對策膜中覆蓋結晶系單元面積之面積未達結晶系單元面積之85%，則覆蓋玻璃所含之鈉離子或鉀離子附著於太陽電池單元而產生PID。As described above, the film of the present invention may be formed by laminating at least the upper portion of the solar cell unit, and may cover at least 85% of the area of the crystal unit. When the area of the area of the crystal unit covered by the PID countermeasure film of the present invention is less than 85% of the area of the crystal unit, the sodium ions or potassium ions contained in the cover glass adhere to the solar cell to generate PID.
藉由使用本發明之PID對策膜而覆蓋太陽電池模組之結晶系單元之表面積之85%以上，可確實地防止太陽電池模組之PID。By using the PID countermeasure film of the present invention to cover 85% or more of the surface area of the crystal unit of the solar cell module, the PID of the solar cell module can be reliably prevented.
以下，使用圖1 至圖3 對本發明之PID 對策膜及使用該膜之太陽電池模組之實施形態進行說明。Hereinafter, an embodiment of the PID countermeasure film of the present invention and a solar battery module using the same will be described with reference to Figs. 1 to 3 .
＜1＞太陽電池用PID對策膜 本發明之太陽電池用PID對策膜之特徵在於：其係防止鹼金屬移動至太陽電池模組內之太陽電池發電元件之接著膜，且係將非晶性之環狀烯烴系共聚物成形為膜狀而成。以下，對本發明之太陽電池用PID對策膜進行詳細說明。<1> PID countermeasure film for solar cells The PID countermeasure film for solar cells of the present invention is characterized in that it prevents the alkali metal from moving to the adhesive film of the solar cell power generation element in the solar cell module, and is amorphous. The cyclic olefin-based copolymer is formed into a film shape. Hereinafter, the PID countermeasure film for a solar cell of the present invention will be described in detail.
＜1-1＞環狀烯烴系樹脂 環狀烯烴系樹脂只要為玻璃轉移溫度為75℃以上、95℃以下且於主鏈中包含源自環狀烯烴之結構單元的聚合物或共聚物，則並無特別限定。例如可列舉：環狀烯烴之加成聚合物或其氫化物、環狀烯烴與乙烯及/或α-烯烴之加成共聚物、或其氫化物等。環狀烯烴系樹脂可單獨使用1種，亦可併用2種以上。又，本發明所使用之環狀烯烴系樹脂之玻璃轉移溫度係依據JISK7121「塑膠之轉移熱測定方法」於升溫速度10℃/min之條件下利用DSC(differential scanning calorimetry，示差掃描熱量測定)進行測定。<1-1> The cyclic olefin resin The cyclic olefin resin is a polymer or copolymer having a glass transition temperature of 75° C. or higher and 95° C. or lower and containing a structural unit derived from a cyclic olefin in the main chain. There is no particular limitation. For example, an addition polymer of a cyclic olefin or a hydrogenated product thereof, an addition copolymer of a cyclic olefin with ethylene and/or an α-olefin, or a hydrogenated product thereof may be mentioned. The cyclic olefin resin may be used alone or in combination of two or more. In addition, the glass transition temperature of the cyclic olefin resin used in the present invention is carried out by DSC (differential scanning calorimetry) under the conditions of a temperature increase rate of 10 ° C/min according to JIS K7121 "Method for measuring transfer heat of plastics". Determination.
作為環狀烯烴系樹脂，包含於在主鏈中包含源自環狀烯烴之結構單元之上述聚合物或上述共聚物中進而接枝及/或共聚合具有極性基之不飽和化合物而成者。The cyclic olefin-based resin is contained in the above-mentioned polymer or a copolymer containing a structural unit derived from a cyclic olefin in the main chain, and further, an unsaturated compound having a polar group is further grafted and/or copolymerized.
作為極性基，例如可列舉：羧基、酸酐基、環氧基、醯胺基、酯基、羥基等，作為具有極性基之不飽和化合物，可列舉：(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐、亞甲基丁二酸酐、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸烷基(碳數1～10)酯、順丁烯二酸烷基(碳數1～10)酯、(甲基)丙烯醯胺、(甲基)丙烯酸2-羥基乙酯等。Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, a decylamino group, an ester group, and a hydroxyl group. Examples of the unsaturated compound having a polar group include (meth)acrylic acid and maleic acid. , maleic anhydride, methylene succinic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10), maleic acid alkyl (carbon number 1 ～10) ester, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and the like.
作為本發明之環狀烯烴系樹脂，亦可使用市售之樹脂。作為市售之環狀烯烴系樹脂，例如可列舉：TOPAS(註冊商標)(TOPAS Advanced Polymers公司製造)、APEL(註冊商標)(三井化學公司製造)，進而，作為以環狀烯烴成分作為起始原料並利用複分解觸媒進行開環聚合、並進行氫化而製造之市售之環狀烯烴系聚合物，可列舉：ZEONEX(註冊商標)(日本ZEON公司製造)、ZEONOR(註冊商標)(日本ZEON公司製造)、ARTON(註冊商標)(JSR公司製造)等。A commercially available resin can also be used as the cyclic olefin resin of the present invention. Examples of the commercially available cyclic olefin-based resin include TOPAS (registered trademark) (manufactured by TOPAS Advanced Polymers Co., Ltd.) and APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.), and further, as a starting point of a cyclic olefin component. The commercially available cyclic olefin-based polymer produced by ring-opening polymerization and hydrogenation using a metathesis catalyst is ZEONEX (registered trademark) (manufactured by ZEON CORPORATION, Japan), and ZEONOR (registered trademark) (Japan ZEON) Manufactured by the company, ARTON (registered trademark) (manufactured by JSR), etc.
本發明之環狀烯烴系樹脂尤佳為使用環狀烯烴系共聚物。其可能因環狀烯烴之開環聚合物或其氫化物中殘留之雙鍵而於加熱環境下發生變色。又，環狀烯烴系共聚物於與EVA之硫化接著中，與環狀烯烴之開環聚合物或其氫化物相比，親和性良好，且接著性優異。 環狀烯烴系共聚物可列舉包含乙烯及/或a-烯烴、及源自下述通式(I)所表示之環狀烯烴之結構單元的共聚物。 [化1](式中，R1 ～R12 可分別相同亦可不同，且係選自由氫原 子、鹵素原子、及烴基所組成之群中， R9 與R10 、R11 與R12 可一體化而形成2價烴基， R9 或R10 與R11 或R12 可相互形成環。 又，n表示0或正整數， 於n為2以上之情形時，R5 ～R8 於各重複單元中可分別相同亦可不同)。 作為a-烯烴，並無特別限制，較佳為碳數2～20之a-烯烴。例如可列舉：丙烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯等。又，該等a-烯烴成分可單獨使用1種亦可同時使用2種以上。 於乙烯及/或a-烯烴中，最佳為單獨使用乙烯。 關於通式(I)所表示之環狀烯烴，R1 ～R12 可分別相同亦可不同，且係選自由氫原子、鹵素原子、及烴基所組成之群中。作為通式(I)所表示之環狀烯烴之具體例，可列舉與日本專利特開2007-302722相同者。 又，環狀烯烴可單獨使用1種，又，亦可將2種以上組合而使用。於該等之中，較佳為單獨使用雙環[2.2.1]庚-2-烯(慣用名：降莰烯(Norbornene))。The cyclic olefin-based resin of the present invention is particularly preferably a cyclic olefin-based copolymer. It may undergo discoloration in a heated environment due to the double bond remaining in the ring-opening polymer of the cyclic olefin or its hydride. Further, in the vulcanization of EVA, the cyclic olefin-based copolymer has a good affinity and a good adhesion property as compared with a ring-opening polymer of a cyclic olefin or a hydrogenated product thereof. The cyclic olefin-based copolymer may, for example, be a copolymer containing ethylene and/or an a-olefin and a structural unit derived from a cyclic olefin represented by the following formula (I). [Chemical 1] (wherein R 1 to R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, R 9 or R 10 and R 11 or R 12 may form a ring with each other. Further, n represents 0 or a positive integer, and when n is 2 or more, R 5 to R 8 may be respectively in each repeating unit. The same or different). The a-olefin is not particularly limited, and is preferably an a-olefin having 2 to 20 carbon atoms. For example, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene , 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-B 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Octadecene, 1-eicosene, and the like. In addition, these a-olefin components may be used alone or in combination of two or more. Among ethylene and/or a-olefin, ethylene is preferably used alone. In the cyclic olefin represented by the formula (I), R 1 to R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Specific examples of the cyclic olefin represented by the formula (I) include the same as those of JP-A-2007-302722. In addition, the cyclic olefin may be used alone or in combination of two or more. Among these, bicyclo[2.2.1]hept-2-ene (common name: Norbornene) is preferably used alone.
對於所使用之聚合觸媒並無特別限定，可使用齊格勒-納他(Ziegler-Natta)系、複分解(Metathesis)系、茂金屬(Metallocene)系觸媒等先前周知之觸媒並藉由周知之方法而獲得。本發明中較佳地使用之環狀烯烴與a-烯烴之加成共聚物或其氫化物較佳為使用茂金屬系觸媒而製造。The polymerization catalyst to be used is not particularly limited, and a conventionally known catalyst such as a Ziegler-Natta system, a metathesis system, or a metallocene catalyst can be used. Obtained by the method of knowing. The addition copolymer of a cyclic olefin and an a-olefin which is preferably used in the present invention or a hydrogenated product thereof is preferably produced by using a metallocene catalyst.
本發明所使用之環狀烯烴系樹脂之製造方法已為公知，例如於日本專利特開平3-45612、日本專利特開昭60-168708、日本專利特開昭62-252406中報告有環狀烯烴之加成聚合物之製造方法，於日本專利特開昭63-145324、日本專利特開昭63-264626、日本專利特開平1-240517中報告有環狀烯烴之開環聚合及其氫化物之製造方法。可藉由依據該等製造方法並適當選擇條件而製造。The method for producing a cyclic olefin-based resin to be used in the present invention is known, and a cyclic olefin is reported in, for example, Japanese Patent Laid-Open No. Hei 3-45162, Japanese Patent Laid-Open No. Hei 60-168708, and Japanese Patent Laid-Open No. Hei 62-252406. The ring-opening polymerization of a cyclic olefin and its hydride are reported in Japanese Patent Laid-Open Publication No. Sho 63-145324, Japanese Patent Laid-Open Publication No. SHO-63-264626 Production method. It can be manufactured by selecting the conditions according to the manufacturing methods.
例如，可於包含乙烯及降莰烯之環狀烯烴共聚物中變更降莰烯含量，藉此合成各種玻璃轉移溫度(Tg)之環狀烯烴系共聚物。若減少降莰烯含量，增加乙烯，則Tg相應地降低。For example, a cyclic olefin-based copolymer having various glass transition temperatures (Tg) can be synthesized by changing the content of norbornene in a cyclic olefin copolymer containing ethylene and norbornene. If the content of norbornene is decreased and ethylene is increased, the Tg is correspondingly lowered.
具有各組成之玻璃轉移溫度(Tg)之聚合物雖然可藉由上述聚合而獲得，亦可藉由市售等級之熔融摻合而獲得。一般而言，於藉由玻璃轉移溫度(Tg)不同之樹脂之摻合而相容之系中，加成性根據摻合比率而成立。於獲得本發明之環狀烯烴樹脂時，除了藉由上述聚合之方法以外，亦可藉由利用擠出機之現有等級之熔融摻合而準備，且發明之效果完全不改變。The polymer having the glass transition temperature (Tg) of each composition can be obtained by the above polymerization, and can also be obtained by melt blending at a commercial grade. In general, in a system which is compatible by blending of resins having different glass transition temperatures (Tg), the addition property is established according to the blending ratio. When the cyclic olefin resin of the present invention is obtained, it can be prepared by melt-blending using the existing grade of the extruder, in addition to the above-mentioned polymerization method, and the effects of the invention are not changed at all.
＜1-3＞其他成分 於本發明之PID對策膜中，亦可調配紫外線吸收劑、受阻胺系穩定劑、耐光穩定劑等以提高耐候性，亦可調配抗氧化劑等以提高長期熱穩定性，亦可調配潤滑劑等以改善膜之成形性。<1-3> Other components In the PID countermeasure film of the present invention, an ultraviolet absorber, a hindered amine stabilizer, a light stabilizer, or the like may be blended to improve weather resistance, and an antioxidant or the like may be formulated to improve long-term heat stability. A lubricant or the like may be formulated to improve the formability of the film.
＜2＞太陽電池模組 本發明之太陽電池模組，其特徵在於：具備上述本發明之太陽電池用之PID對策膜。<2> Solar battery module The solar battery module of the present invention is characterized by comprising the above-described PID countermeasure film for a solar battery of the present invention.
圖1係表示本發明之太陽電池模組之一例之示意剖視圖。圖1所示之太陽電池模組100係自作為受光側之表面基板之透明玻璃板11起依序具有現有之密封膜18、本發明之PID對策膜14、現有之密封膜18、太陽電池元件15、現有之密封膜18、及背部片材12而組成。背部片材部分亦可為覆蓋玻璃。此時為如圖2之太陽電池模組200。即，成為相對於太陽電池元件15而上下對稱之構成。以上之圖1及圖2所示之太陽電池模組之構成係為一例，本發明之太陽電池模組並不限定於該構成。Fig. 1 is a schematic cross-sectional view showing an example of a solar battery module of the present invention. The solar cell module 100 shown in FIG. 1 has a conventional sealing film 18, a PID countermeasure film 14 of the present invention, a conventional sealing film 18, and a solar cell element, respectively, from a transparent glass plate 11 as a surface substrate on a light receiving side. 15. The conventional sealing film 18 and the back sheet 12 are composed. The back sheet portion may also be a cover glass. At this time, it is the solar battery module 200 of FIG. In other words, it is configured to be vertically symmetrical with respect to the solar cell element 15. The configuration of the solar battery module shown in FIGS. 1 and 2 above is an example, and the solar battery module of the present invention is not limited to this configuration.
作為本發明之太陽電池模組所使用之太陽電池元件並無特別限定，可使用單晶矽、多晶矽、非晶矽等矽系、第III-V族或第II-VI族化合物(鎵-砷、銅-銦-硒、銅-銦-鎵-硒、鎘-銻等)等化合物半導體系等之各種太陽電池元件。The solar cell element used in the solar cell module of the present invention is not particularly limited, and a lanthanide group, a group III-V group or a group II-VI compound (gallium-arsenic) such as single crystal germanium, polycrystalline germanium or amorphous germanium can be used. Various solar cell elements such as compound semiconductors such as copper-indium-selenium, copper-indium-gallium-selenium, and cadmium-tellurium.
又，於本發明之太陽電池模組中，於使用玻璃作為透明基材之情形時，作為太陽光受光側之表面基板可為釋放鈉離子之白板玻璃，亦可為玻璃表面經鉀離子置換之化學強化玻璃。自玻璃釋放之金屬離子被本發明之PID對策膜所防禦，太陽電池單元受到保護而不發生PID。Further, in the solar cell module of the present invention, when glass is used as the transparent substrate, the surface substrate which is the light receiving side of the sunlight may be a white glass which releases sodium ions, or the surface of the glass may be replaced by potassium ions. Chemically strengthened glass. The metal ions released from the glass are protected by the PID countermeasure film of the present invention, and the solar cell unit is protected from the PID.
再者，可將本發明之PID對策膜用於使用丙烯酸系樹脂、聚碳酸酯、聚酯、含氟樹脂等作為太陽電池模組之透明基板的太陽電池模組。Further, the PID countermeasure film of the present invention can be used as a solar cell module using a transparent substrate of a solar cell module such as an acrylic resin, a polycarbonate, a polyester, or a fluorine-containing resin.
又，作為相反側之背部片材，可列舉樹脂膜或金屬膜等單層或多層膜，例如作為樹脂膜，可列舉氟樹脂膜、PET(聚對苯二甲酸乙二酯)樹脂膜、PBT(聚對苯二甲酸丁二酯)樹脂膜等，作為金屬膜，可列舉鋁、不鏽鋼等之膜。 [實施例]Further, examples of the back sheet on the opposite side include a single layer or a multilayer film such as a resin film or a metal film. Examples of the resin film include a fluororesin film, a PET (polyethylene terephthalate) resin film, and a PBT. A (polybutylene terephthalate) resin film or the like, and examples of the metal film include films of aluminum and stainless steel. [Examples]
以下，藉由實施例更具體地對本發明進行說明，但本發明並不限定於以下實施例。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.
作為以下實施例中所使用之環狀烯烴系樹脂，向將TOPAS Advanced Polymers公司製造之TOPAS8007S-04(玻璃轉移溫度78℃)及TOPAS6013M-07(玻璃轉移溫度130℃)之2種以某一摻合比率混合而成之混合物內調配微量之紫外線抑制劑及耐光穩定劑，而製作具有所需之玻璃轉移溫度(Tg)及厚度之PID對策膜。使用所獲得之PID對策膜，藉由以下方法製作圖1之構成之太陽電池模組100。再者，於製造太陽電池模組時，由於利用層壓裝置進行，故而於層壓裝置之熱板上將圖1之上下顛倒並積層各構件。As a cyclic olefin-based resin used in the following examples, TOPAS 8007S-04 (glass transition temperature: 78 ° C) and TOPAS 6013 M-07 (glass transition temperature: 130 ° C) manufactured by TOPAS Advanced Polymers Co., Ltd. were mixed. A mixture of a mixture of a mixture of a UV inhibitor and a light stabilizer is prepared to prepare a PID countermeasure film having a desired glass transition temperature (Tg) and thickness. Using the obtained PID countermeasure film, the solar cell module 100 of the configuration of Fig. 1 was produced by the following method. Further, in the manufacture of the solar cell module, since it is carried out by means of a laminating apparatus, the upper and lower sides of Fig. 1 are inverted on the hot plate of the laminating apparatus and the members are laminated.
[實施例1] 使用日本製鋼所製造之雙軸擠出機TEX-30a，於熔融樹脂溫度200℃下將作為紫外線吸收劑之2-羥基4-正辛氧基二苯甲酮0.4重量份、作為耐光穩定劑之雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯0.2重量份與作為環狀烯烴系樹脂之100重量份之TOPAS8007S-04進行混練，而獲得環狀烯烴系樹脂組合物顆粒。繼而，將該顆粒投入至具備寬度300 mm之T型模頭的單軸擠出成形機中，且將T型模頭部之樹脂溫度設為140℃，而製作玻璃轉移溫度為78℃且厚度60 μm之PID對策膜(環狀烯烴系樹脂膜)。使用所獲得之PID對策膜，藉由以下方法製作太陽電池模組。[Example 1] 0.4 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone as a UV absorber at a molten resin temperature of 200 ° C using a twin-screw extruder TEX-30a manufactured by Nippon Steel Co., Ltd. 0.2 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate as a light stabilizer, and kneaded with TOPAS 8007S-04 as a 100 parts by weight of a cyclic olefin resin. Further, particles of the cyclic olefin resin composition were obtained. Then, the pellet was placed in a uniaxial extrusion molding machine having a T-die having a width of 300 mm, and the resin temperature of the T-die head was set to 140 ° C, and the glass transition temperature was 78 ° C and the thickness was made. PID countermeasure film (cyclic olefin resin film) of 60 μm. Using the obtained PID countermeasure film, a solar cell module was produced by the following method.
太陽電池模組100係於覆蓋玻璃11上準備三井化學公司製造之450 μm之快速固化型(EVA-1)作為密封膜18。於其上依序積層本實施例中所製作之PID對策膜(環狀烯烴系樹脂膜)14，且於該PID對策膜14上積層密封膜18(EVA-1)、太陽電池結晶系單元、密封膜18(EVA-1)、作為背面材(背部片材)12之東洋鋁公司製造之PET系背部片材。使用真空貼合機(Nisshinbo Mechatronics股份有限公司製造，製品名：PVL1537N)於熱板溫度：150℃、加工時間22分鐘(詳細內容，抽真空：5分鐘，壓製：2分鐘，壓力保持：15分鐘)之條件下對該積層體進行壓製加工。與端子盒連接之配線部分係自於背面材預先設置有裂口之部分拉出，利用焊料進行固定，並利用聚矽氧灌封材填滿直至遮蔽二極體，而形成蓋。灌封材係使用Dow-Corning公司製造之PV-7311。對於玻璃邊緣部，不應用邊緣密封件，而是利用使用三井化學公司製造之TPV：MILASTOMER材之襯墊而填埋與鋁框之間隙。The solar cell module 100 is attached to the cover glass 11 as a sealing film 18 of a 450 μm rapid curing type (EVA-1) manufactured by Mitsui Chemicals. A PID countermeasure film (cyclic olefin resin film) 14 produced in the present embodiment is laminated thereon, and a sealing film 18 (EVA-1) and a solar cell crystal unit are laminated on the PID countermeasure film 14. A sealing film 18 (EVA-1) and a PET-based back sheet manufactured by Toyo Aluminum Co., Ltd. as a back sheet (back sheet) 12. Using a vacuum laminator (manufactured by Nisshinbo Mechatronics Co., Ltd., product name: PVL1537N) at a hot plate temperature: 150 ° C, processing time 22 minutes (details, vacuum: 5 minutes, pressing: 2 minutes, pressure holding: 15 minutes) The laminate is subjected to press processing under the conditions. The wiring portion connected to the terminal box is pulled out from a portion in which the back material is previously provided with a slit, fixed by solder, and filled with a polysilicone potting material until the diode is shielded to form a cover. The potting material was PV-7311 manufactured by Dow-Corning. For the edge portion of the glass, the edge seal was not applied, but the gap between the aluminum frame and the aluminum frame was filled using a liner of TPV: MILASTOMER material manufactured by Mitsui Chemicals.
[實施例2] 於實施例2中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS8007S-04 90重量份及TOPAS6013M-07 10重量份以外，與實施例1同樣地製作玻璃轉移溫度為80℃且厚度為75 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Example 2] In Example 2, except that 100 parts by weight of TOPAS8007S-04 as the cyclic olefin resin of Example 1 was changed to TOPAS8007S-04 90 parts by weight and TOPAS6013M-07 10 parts by weight, and Examples 1 A PID countermeasure film having a glass transition temperature of 80 ° C and a thickness of 75 μm was produced in the same manner. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[實施例3] 於實施例3中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS8007S-04 72重量份及TOPAS6013M-07 28重量份以外，與實施例1同樣地製作玻璃轉移溫度為90℃且厚度為100 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Example 3] In Example 3, except that 100 parts by weight of TOPAS8007S-04 as the cyclic olefin resin of Example 1 was changed to TOPAS8007S-04 72 parts by weight and TOPAS6013M-07 28 parts by weight, and Examples 1 A PID countermeasure film having a glass transition temperature of 90 ° C and a thickness of 100 μm was produced in the same manner. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[實施例4] 於實施例4中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS8007S-04 67重量份及TOPAS6013M-07 33重量份以外，與實施例1同樣地製作玻璃轉移溫度為93℃且厚度為125 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Example 4] In Example 4, except that 100 parts by weight of TOPAS 8007S-04 as the cyclic olefin resin of Example 1 was changed to TOPAS8007S-04 67 parts by weight and TOPAS6013M-07 33 parts by weight, and Examples 1 A PID countermeasure film having a glass transition temperature of 93 ° C and a thickness of 125 μm was produced in the same manner. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[實施例5] 於實施例5中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS8007S-04 72重量份及TOPAS6013M-07 28重量份以外，與實施例1同樣地製作玻璃轉移溫度為90℃且厚度為75 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。再者，此時將PID對策膜如圖5所示般僅配置於將複數片太陽電池單元連接而成之電池串W上(覆蓋玻璃側)而製造太陽電池模組。因此，為於覆蓋玻璃側之電池串W之行間未設置PID對策膜之構成。[Example 5] In Example 5, except that 100 parts by weight of TOPAS8007S-04 as the cyclic olefin resin of Example 1 was changed to TOPAS8007S-04 72 parts by weight and TOPAS6013M-07 28 parts by weight, and Examples 1 A PID countermeasure film having a glass transition temperature of 90 ° C and a thickness of 75 μm was produced in the same manner. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film. Further, at this time, as shown in FIG. 5, the PID countermeasure film is disposed only on the battery string W (covering the glass side) in which a plurality of solar battery cells are connected to each other to manufacture a solar battery module. Therefore, the configuration of the PID countermeasure film is not provided between the rows of the battery strings W covering the glass side.
[比較例1] 於比較例1中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS8007S-04 59重量份及TOPAS6013M-07 41重量份以外，與實施例1同樣地製作玻璃轉移溫度為98℃且厚度為200 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Comparative Example 1] In Comparative Example 1, except that 100 parts by weight of TOPAS 8007S-04 as the cyclic olefin resin of Example 1 was changed to TOPAS8007S-04 59 parts by weight and TOPAS6013M-07 41 parts by weight, and Examples 1 A PID countermeasure film having a glass transition temperature of 98 ° C and a thickness of 200 μm was produced in the same manner. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[比較例2] 於比較例2中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS6013M-07 100重量份以外，與實施例1同樣地製作玻璃轉移溫度為142℃且厚度為100 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Comparative Example 2] A glass transition temperature was produced in the same manner as in Example 1 except that 100 parts by weight of TOPAS 8007S-04 as the cyclic olefin resin of Example 1 was changed to 100 parts by weight of TOPAS 6013M-07. A PID countermeasure film of 142 ° C and a thickness of 100 μm. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[比較例3] 於比較例3中，嘗試利用作為實施例1之環狀烯烴系樹脂之TOPAS8007S-04而製作玻璃轉移溫度為78℃且厚度為30 μm之PID對策膜。無法進行膜之捲取，未獲得PID對策膜。[Comparative Example 3] In Comparative Example 3, a PID countermeasure film having a glass transition temperature of 78 ° C and a thickness of 30 μm was produced by using TOPAS 8007S-04 as the cyclic olefin resin of Example 1. The film was not taken up, and the PID countermeasure film was not obtained.
[比較例4] 於比較例4中，除了將實施例1之作為環狀烯烴系樹脂之TOPAS8007S-04 100重量份變更為TOPAS6013M-07 100重量份以外，與實施例1同樣地製作玻璃轉移溫度為142℃且厚度250 μm之PID對策膜。使用所獲得之PID對策膜，藉由與實施例1相同之方法而製作太陽電池模組。[Comparative Example 4] A glass transition temperature was produced in the same manner as in Example 1 except that 100 parts by weight of TOPAS 8007S-04 as the cyclic olefin resin of Example 1 was changed to 100 parts by weight of TOPAS 6013M-07. A PID countermeasure film of 142 ° C and a thickness of 250 μm. A solar cell module was produced in the same manner as in Example 1 using the obtained PID countermeasure film.
[比較例5] 比較例5係不使用本實施例之使用有環狀烯烴系樹脂之PID對策膜的先前之太陽電池模組900。其係圖4所示之先前型太陽電池模組，所使用之構件與實施例1相同，且係不具有圖1之PID對策膜14之構成。[Comparative Example 5] In Comparative Example 5, the prior solar battery module 900 using the PID countermeasure film of the cyclic olefin resin of the present Example was not used. The front type solar cell module shown in FIG. 4 is the same as that of the first embodiment, and does not have the configuration of the PID countermeasure film 14 of FIG.
[PID對策膜之成形性] 針對實施例1至實施例5、及比較例1至比較例4所製成之PID對策膜之膜成型性，根據以下指標對自3吋支幹之最末端起10 m之面積(寬度1 m)對微裂縫及皺褶進行評價。將其評價結果示於表1。 ＜微裂縫＞ 評價分 3分：完全無微裂縫。 評價分 2分：於模組總面積之20%以下之面積存在微裂縫。 評價分 1分：於60%以上之面積存在微裂縫。 所謂片材微裂縫係指與利用錘等敲破玻璃時形成於玻璃內部之無數破裂相同狀態者。 ＜皺褶之存在部位數＞ 皺褶之存在部位數係對100 m捲之PID對策膜之外觀進行觀察。所謂皺褶係以肉眼容易辨識之大小，設為寬度1 mm以上、長度30 mm以上。 評價分 3分：無皺褶，平滑。 評價分 2分：存在1處皺褶。 評價分 1分：存在2處以上之皺褶。[Formability of the PD countermeasure film] The film moldability of the PID countermeasure film produced in the first to fifth embodiments and the comparative example 1 to the comparative example 4 was based on the following indexes from the end of the 3 吋 branch The area of 10 m (width 1 m) was evaluated for microcracks and wrinkles. The evaluation results are shown in Table 1. <Microcrack> Evaluation score 3 points: no micro cracks at all. Evaluation points 2 points: There are micro cracks in the area below 20% of the total area of the module. Evaluation score 1 point: micro cracks exist in more than 60% of the area. The sheet microcrack refers to the same state as the numerous cracks formed inside the glass when the glass is broken by a hammer or the like. <The number of the parts of the wrinkles> The number of the parts of the wrinkles is observed on the appearance of the 100 m roll of the PID countermeasure film. The wrinkle is a size that is easily recognized by the naked eye and has a width of 1 mm or more and a length of 30 mm or more. Evaluation score 3 points: no wrinkles, smooth. Evaluation score 2 points: There is 1 wrinkle. Evaluation score 1 point: There are more than 2 wrinkles.
[PID對策膜之模組成形性] 針對使用實施例1至實施例5、及比較例1至比較例4中所製成之PID對策膜之太陽電池模組之成型性，對48直之太陽電池模組自受光面側進行觀察，且根據以下指標對微裂縫及痘痕(pockmark)進行評價。將其評價結果示於表1。 ＜微裂縫＞ 評價分 3分：完全無微裂縫。 評價分 2分：於總面積之5%以下存在微裂縫。 評價分 1分：於總面積之10%以上存在微裂縫。 ＜痘痕個數＞ 所謂痘痕係PID對策膜上之圓形之皺褶，設為半徑500 μm以上者。 評價分 3分：完全無痘痕。 評價分 2分：痘痕為5個以下。 評價分 1分：痘痕為6個以上。[Module Formability of PID Countermeasure Film] For the moldability of the solar cell module using the PID countermeasure film produced in Examples 1 to 5 and Comparative Examples 1 to 4, 48 solar cells were used. The module was observed from the light-receiving side, and microcracks and pockmarks were evaluated according to the following indicators. The evaluation results are shown in Table 1. <Microcrack> Evaluation score 3 points: no micro cracks at all. The evaluation score is 2 points: micro cracks exist below 5% of the total area. Evaluation score: 1 minute: There are micro cracks in more than 10% of the total area. <The number of the acne scars> The acne scar is a round wrinkle on the film of the PID countermeasure, and the radius is 500 μm or more. Evaluation score 3 points: completely no acne marks. Evaluation points 2 points: 5 or less pock marks. Evaluation score: 1 point: 6 or more pock marks.
[PID試驗] 對於實施例1至實施例5、及比較例1至比較例5中所製作之太陽電池模組，如下所述般實施PID試驗。[PID Test] For the solar cell modules produced in Examples 1 to 5 and Comparative Examples 1 to 5, a PID test was carried out as follows.
利用太陽模擬器測定預先製作之太陽電池模組之輸出。其後，於ESPEC公司製造之PID試驗裝置中，放入85℃、85%濕度之腔室中並施加2500小時之-1000 V之電壓之後，取出太陽電池模組，再次利用太陽模擬器測定輸出。藉由下式算出太陽電池模組之發電劣化度。 發電劣化度(%)＝[(起始最高輸出－PID試驗後之最高輸出)/(起始最高輸出)]×100The output of the pre-made solar cell module was measured using a solar simulator. Thereafter, in a PID test apparatus manufactured by ESPEC, placed in a chamber of 85 ° C and 85% humidity and applied a voltage of -500 V for 2500 hours, the solar cell module was taken out, and the output was measured again using a solar simulator. . The degree of deterioration of power generation of the solar cell module was calculated by the following formula. Power deterioration degree (%) = [(starting maximum output - highest output after PID test) / (starting maximum output)] × 100
再者，於PID試驗中，將鋁板配置於太陽電池模組之覆蓋玻璃上，測定產生於鋁板與太陽電池模組之輸出端子之間的漏電流。於表1中，作為PID試驗結果，記載有各實施例及比較例之PID試驗開始1000小時後之漏電流之測定結果。Furthermore, in the PID test, an aluminum plate was placed on the cover glass of the solar cell module, and the leakage current generated between the aluminum plate and the output terminal of the solar cell module was measured. In Table 1, as a result of the PID test, the measurement results of the leak current after 1000 hours from the start of the PID test of each of the examples and the comparative examples are described.
將實施例1至實施例5、及比較例1至比較例5中所製作之太陽電池模組之上述PID試驗之結果示於表1。根據表1可知，使用本發明之PID對策膜之實施例1至實施例5之太陽電池模組完全不存在因PID所致之發電劣化，且圖3表示發電劣化隨著時間經過如何變化。圖3之橫軸為OID試驗時間，縱軸表示發電能力保持率(%)。該發電能力保持率係自100%減去發電劣化度(%)所得之數值，若為100%，則表示完全未產生發電劣化。比較例5之未使用PID對策膜之太陽電池模組可知於短時間內成為零輸出。 [產業上之可利用性]The results of the above-described PID tests of the solar cell modules produced in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1. According to Table 1, it is understood that the solar cell modules of Examples 1 to 5 using the PID countermeasure film of the present invention have no power generation deterioration due to PID, and FIG. 3 shows how the power generation deterioration changes with time. The horizontal axis of Fig. 3 is the OID test time, and the vertical axis represents the power generation capacity retention rate (%). The power generation capacity retention rate is a value obtained by subtracting the power generation deterioration degree (%) from 100%, and if it is 100%, it means that power generation deterioration is not generated at all. In the solar cell module of Comparative Example 5 in which the PID countermeasure film was not used, it was found that the output was zero output in a short time. [Industrial availability]
根據本發明，對於太陽電池發電站，由於可在實地於至少20年間防止因PID現象所致之發電劣化，故而可作為具有與火力發電站或水力發電站相同壽命之發電站而發電。According to the present invention, in the solar cell power station, since power generation deterioration due to the PID phenomenon can be prevented in the field for at least 20 years, power generation can be performed as a power station having the same life as that of a thermal power plant or a hydroelectric power station.
11‧‧‧覆蓋玻璃
12‧‧‧背面材(背部片材)
14‧‧‧PID對策膜(環狀烯烴系樹脂膜)
15‧‧‧結晶系單元(太陽電池單元)
18‧‧‧密封膜(EVA等)
100‧‧‧太陽電池模組
200‧‧‧太陽電池模組
900‧‧‧先前型太陽電池模組
W‧‧‧電池串11‧‧‧ Covering glass
12‧‧‧Back material (back sheet)
14‧‧‧Pd countermeasure film (cyclic olefin resin film)
15‧‧‧ Crystallization unit (solar battery unit)
18‧‧‧ Sealing film (EVA, etc.)
100‧‧‧Solar battery module
200‧‧‧Solar battery module
900‧‧‧Previous solar cell module
W‧‧‧Battery string
圖1 係表示本發明之太陽電池模組之構成例1 之示意剖視圖。 圖2 係表示本發明之太陽電池模組之構成例2 之示意剖視圖。 圖3 係本發明之太陽電池模組與先前之太陽電池之劣化程度之說明圖。 圖4 係表示先前之太陽電池模組之構成之示意剖視圖。 圖5 係實施例5 之太陽電池模組之構成之說明圖。Fig. 1 is a schematic cross-sectional view showing a configuration example 1 of a solar battery module of the present invention. Fig. 2 is a schematic cross-sectional view showing a configuration example 2 of a solar battery module of the present invention. Fig. 3 is an explanatory view showing the degree of deterioration of the solar cell module of the present invention and the prior solar cell. Fig. 4 is a schematic cross-sectional view showing the configuration of a prior solar cell module. Fig. 5 is an explanatory view showing the configuration of a solar battery module of the fifth embodiment.
11‧‧‧覆蓋玻璃 11‧‧‧ Covering glass
12‧‧‧背面材(背部片材) 12‧‧‧Back material (back sheet)
14‧‧‧PID對策膜(環狀烯烴系樹脂膜) 14‧‧‧Pd countermeasure film (cyclic olefin resin film)
15‧‧‧結晶系單元(太陽電池單元) 15‧‧‧ Crystallization unit (solar battery unit)
18‧‧‧密封膜(EVA等) 18‧‧‧ Sealing film (EVA, etc.)
100‧‧‧太陽電池模組 100‧‧‧Solar battery module
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014032616 | 2014-02-24 | ||
| JP2015028550A JP5965004B2 (en) | 2014-02-24 | 2015-02-17 | PID countermeasure film for solar cell and PID countermeasure solar cell module using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201547034A true TW201547034A (en) | 2015-12-16 |
Family
ID=53878444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104105848A TW201547034A (en) | 2014-02-24 | 2015-02-24 | Anti-PID film for solar cell and anti-PID solar cell module using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5965004B2 (en) |
| CN (1) | CN106170871A (en) |
| TW (1) | TW201547034A (en) |
| WO (1) | WO2015125948A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022086058A (en) * | 2020-11-30 | 2022-06-09 | 株式会社リコー | Photoelectric conversion element, photoelectric conversion module, electronic equipment, and power supply module |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08306948A (en) * | 1995-04-28 | 1996-11-22 | Kureha Chem Ind Co Ltd | Surface protective layer for solar cell module |
| JP2000106450A (en) * | 1998-09-29 | 2000-04-11 | Nippon Zeon Co Ltd | Solar cell module and protective sheet therefor |
| JP2006198922A (en) * | 2005-01-21 | 2006-08-03 | Mitsui Chemicals Inc | Protective sheet for solar battery module and solar battery module |
| WO2011129869A1 (en) * | 2010-04-15 | 2011-10-20 | Topas Advanced Polymers, Inc. | Melt blends of amorphous cycloolefin polymers and partially crystalline cycloolefin elastomers with improved toughness |
| JP2014022473A (en) * | 2012-07-13 | 2014-02-03 | Nisshinbo Holdings Inc | Solar cell module |
-
2015
- 2015-02-17 JP JP2015028550A patent/JP5965004B2/en active Active
- 2015-02-23 WO PCT/JP2015/054921 patent/WO2015125948A1/en active Application Filing
- 2015-02-23 CN CN201580019397.1A patent/CN106170871A/en active Pending
- 2015-02-24 TW TW104105848A patent/TW201547034A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN106170871A (en) | 2016-11-30 |
| JP2015173262A (en) | 2015-10-01 |
| JP5965004B2 (en) | 2016-08-03 |
| WO2015125948A1 (en) | 2015-08-27 |
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