WO2012091004A1 - Protective sheet for back surface of solar cell modules, production method for protective sheet, and solar cell module - Google Patents
Protective sheet for back surface of solar cell modules, production method for protective sheet, and solar cell module Download PDFInfo
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- WO2012091004A1 WO2012091004A1 PCT/JP2011/080197 JP2011080197W WO2012091004A1 WO 2012091004 A1 WO2012091004 A1 WO 2012091004A1 JP 2011080197 W JP2011080197 W JP 2011080197W WO 2012091004 A1 WO2012091004 A1 WO 2012091004A1
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- back surface
- solar cell
- protective sheet
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- 230000001681 protective effect Effects 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 21
- 239000005060 rubber Substances 0.000 claims abstract description 21
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- 238000010248 power generation Methods 0.000 claims description 10
- 229920002379 silicone rubber Polymers 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 241000872198 Serjania polyphylla Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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Images
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
- H01L31/049—Protective back sheets
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
The present invention addresses the problem of providing: a protective sheet for the back surface of solar cell modules which is not susceptible to delamination even if exposed to high-temperature, high-humidity conditions for an extended period, and which exhibits high electrical resistance, low thermal shrinkage and low water-vapor permeability; a production method for the protective sheet; and a solar cell module. The present invention is a protective sheet for the back surface of solar cell modules which comprises a polybutylene terephthalate resin, has a thickness of 200-500 μm when unstretched, and exhibits a thermal shrinkage of at most 1.5% in the take-off direction and the direction perpendicular thereto at a temperature of 150°C. The protective sheet according to the present invention is manufactured by extruding a polybutylene terephthalate resin by means of a flat die, and passing the extruded sheet through the nip between a rubber roll and a metal roll having a preset surface temperature in the range of 25-90°C.
Description
本発明は、新規の太陽電池モジュール用裏面保護シート、その製造方法、および該裏面保護シートを備えた太陽電池モジュールに関するものである。
The present invention relates to a novel back surface protection sheet for solar cell modules, a method for producing the back surface protection sheet, and a solar cell module including the back surface protection sheet.
近年、環境問題への意識の高まりにより、クリーンエネルギーを利用した発電手段の一つとして、太陽電池モジュールを備えた太陽電池発電システムが普及している。太陽電池モジュールは板状の太陽電池素子が多数配置されており、これらの素子を封止材と呼ばれるエチレン－酢酸ビニル共重合体で挟み込み、太陽光が当る側にガラスなどの前面板が、反対側には太陽電池モジュール用裏面保護シート（以下、裏面保護シートと略記する）がこの順に重ね合わされる。そして、真空加熱ラミネーション法などにより一体成形されている。
2. Description of the Related Art In recent years, solar cell power generation systems equipped with solar cell modules have become widespread as one of power generation means using clean energy due to increasing awareness of environmental issues. A large number of plate-like solar cell elements are arranged in the solar cell module. These elements are sandwiched by an ethylene-vinyl acetate copolymer called a sealing material, and the front plate such as glass is opposite to the side where the sunlight hits. On the side, a back surface protection sheet for solar cell modules (hereinafter abbreviated as back surface protection sheet) is superposed in this order. And it is integrally molded by a vacuum heating lamination method or the like.
この裏面保護シートは、発電素子や封止材を保護するものであって、外部からの機械的衝撃、圧力から発電素子を保護し、水分の浸透を防いで発電素子の劣化を防ぐなどの特性が要求されている。そのため、裏面保護シートは、電気絶縁性が高く、熱収縮率が小さく、高温高湿中に長期間放置されても裏面保護シート自身が層間剥離しない耐久性、さらに封止材との界面で剥離しない等の特性が要求されている。
This back surface protection sheet protects the power generation element and the sealing material, and protects the power generation element from external mechanical shock and pressure, preventing moisture penetration and preventing deterioration of the power generation element. Is required. Therefore, the back protection sheet has high electrical insulation, low thermal shrinkage, durability that prevents the back protection sheet itself from delaminating even when left in high temperature and high humidity, and peeling at the interface with the sealing material Characteristics such as not being required are required.
前述のように、裏面保護シートには、高い電気絶縁性が求められており、そのためには相応の厚みが必要である。また、水分透過率を下げるためにも、裏面保護シートは厚い方が有利であり、ポリフッ化ビニルフィルムとポリエチレンテレフタレートフィルムとを接着剤で貼り合せた裏面保護シート、基材フィルムと金属や金属酸化物などの蒸着層を設けたバリア性フィルムとを接着剤で貼合した裏面保護シートが提案されている。例えば特開２００５－３２２６８７号公報（特許文献１）には、基材フィルムであるポリエチレンテレフタレートフィルムの両面へアルミニウム蒸着層を設けてバリアシートとし、ポリウレタン系接着剤で２枚のバリアシートを積層した裏面保護シートが開示されているが、当該接着剤層は高温高湿下に長期間暴露されると剥離する恐れがあった。
As described above, the back surface protection sheet is required to have high electrical insulation, and for this purpose, an appropriate thickness is required. In addition, in order to reduce moisture permeability, it is advantageous that the back protection sheet is thick, and the back protection sheet, base film and metal or metal oxide film, which are obtained by bonding a polyvinyl fluoride film and a polyethylene terephthalate film with an adhesive. A back surface protection sheet in which a barrier film provided with a vapor deposition layer such as an object is bonded with an adhesive has been proposed. For example, in Japanese Patent Application Laid-Open No. 2005-322687 (Patent Document 1), an aluminum vapor deposition layer is provided on both surfaces of a polyethylene terephthalate film as a base film to form a barrier sheet, and two barrier sheets are laminated with a polyurethane adhesive. Although a back surface protective sheet is disclosed, the adhesive layer may be peeled off when exposed to a high temperature and high humidity for a long period of time.
これに対し、特開２００８－４６９１号公報（特許文献２）には、少なくとも２層以上の基材を特定のポリウレタン系接着剤を用いて貼り合せた裏面保護シートは、ハイプレッシャークッカー（加圧蒸気による促進評価装置）で少なくとも１０５℃－１６８時間暴露後でも基材間の浮きを伴わず、１Ｎ／１５ｍｍ以上のラミネート強度を維持することが記載されているが、この接着剤を使用しても暴露期間が長くなるに従ってラミネート強度は低下しており、この接着剤で接着した裏面保護シートでも長期間使用すると層間剥離の恐れがある。すなわち、接着剤で貼合した裏面保護シートは、高温高湿下に長期間暴露されると剥離強度が大幅に低下し、剥離する恐れがあるのが現状である。
On the other hand, Japanese Patent Application Laid-Open No. 2008-4691 (Patent Document 2) discloses a back pressure protection sheet in which at least two layers of substrates are bonded using a specific polyurethane-based adhesive. It is described that a laminate strength of 1 N / 15 mm or more is maintained without floating between substrates even after exposure to at least 105 ° C. for 168 hours using a steam acceleration evaluation apparatus. However, as the exposure period becomes longer, the laminate strength decreases, and there is a risk of delamination if the back protective sheet adhered with this adhesive is used for a long period of time. That is, the present situation is that the back surface protection sheet bonded with an adhesive has a possibility that the peel strength is greatly lowered and peeled when exposed to a high temperature and high humidity for a long time.
これを解決するには、裏面保護シートとして接着剤を使わない厚い単層のシートを用いれば良いのであるが、裏面保護シートの基材として通常用いられているポリエチレンテレフタレートは製膜後二軸延伸加工をしなければ実用に供しうるフィルムとならず、結果として厚さが２００μｍ未満のフィルムしか得られないのが現状である。従って、裏面保護シートに要望される電気絶縁性、具体的には、後述する最大許容システム電圧が１０００Ｖ以上である裏面保護シートを得るには、上記のように複数枚のポリエチレンテレフタレートフィルム等を接着剤で貼合せざるを得なかった。
To solve this, it is sufficient to use a thick single-layer sheet that does not use an adhesive as the back surface protection sheet, but polyethylene terephthalate, which is normally used as a base material for the back surface protection sheet, is biaxially stretched after film formation. If not processed, the film cannot be used practically, and as a result, only a film having a thickness of less than 200 μm can be obtained. Therefore, in order to obtain the electrical insulation required for the back surface protection sheet, specifically, the back surface protection sheet whose maximum allowable system voltage described later is 1000 V or more, a plurality of polyethylene terephthalate films or the like are bonded as described above. I had to paste it together with the agent.
一方、ポリブチレンテレフタレートは、延伸することなく実用に供しうるフィルムが得られるものの、２００μｍ以上の厚みの厚いフィルムを得ようとすると、フラットダイから押出された溶融樹脂を冷却ロールに接触させる際、全幅に渡って均一に同時に接触させるのが難しく、先に冷却ロールに接触した部分が冷却され結晶化すると、その隣接部分に浮きが生じて、結果として部分的に冷却速度が異なるため平滑なフィルムが得られないという問題があった。
On the other hand, polybutylene terephthalate can be used for practical use without stretching, but when trying to obtain a thick film of 200 μm or more, when contacting the molten resin extruded from the flat die to the cooling roll, It is difficult to make uniform contact over the entire width at the same time, and when the portion that has previously contacted the cooling roll is cooled and crystallized, floating occurs in the adjacent portion, resulting in a partially different cooling rate, resulting in a smooth film There was a problem that could not be obtained.
本発明はこのような問題に鑑みなされたもので、高温高湿下に長期間暴露されても層間剥離の恐れがなく、電気絶縁性が高く、熱収縮率、水蒸気透過度が小さい太陽電池モジュール用裏面保護シート、その製造方法、及びそれを用いた太陽電池モジュールを提供することを課題とする。
The present invention has been made in view of such problems, and there is no risk of delamination even when exposed to a high temperature and high humidity for a long period of time. The solar cell module has high electrical insulation, low thermal shrinkage, and low water vapor permeability. It is an object of the present invention to provide a backside protective sheet for use, a manufacturing method thereof, and a solar cell module using the same.
本発明者らは、ポリブチレンテレフタレートを特定の押出し成形方法でシートとすることにより、優れた特性を有する新規の太陽電池モジュール用裏面保護シートが得られることを見出し、本発明を完成するに到った。
The present inventors have found that a novel back surface protection sheet for solar cell modules having excellent characteristics can be obtained by forming polybutylene terephthalate into a sheet by a specific extrusion molding method, and the present invention has been completed. It was.
すなわち、本発明によれば、
ポリブチレンテレフタレート系樹脂からなり、無延伸であるとともに、厚さが２００μｍ～５００μｍであり、且つ１５０℃における熱収縮率が引取り方向およびそれに直交する方向共に１．５％以下であることを特徴とする太陽電池モジュール用裏面保護シートが提供される。 That is, according to the present invention,
It is made of polybutylene terephthalate resin, is unstretched, has a thickness of 200 μm to 500 μm, and has a heat shrinkage rate at 150 ° C. of 1.5% or less in both the take-up direction and the direction perpendicular thereto. The back surface protection sheet for solar cell modules is provided.
ポリブチレンテレフタレート系樹脂からなり、無延伸であるとともに、厚さが２００μｍ～５００μｍであり、且つ１５０℃における熱収縮率が引取り方向およびそれに直交する方向共に１．５％以下であることを特徴とする太陽電池モジュール用裏面保護シートが提供される。 That is, according to the present invention,
It is made of polybutylene terephthalate resin, is unstretched, has a thickness of 200 μm to 500 μm, and has a heat shrinkage rate at 150 ° C. of 1.5% or less in both the take-up direction and the direction perpendicular thereto. The back surface protection sheet for solar cell modules is provided.
本発明は、また、ポリブチレンテレフタレート系樹脂をフラットダイより押出し、押出したシートをゴムロールと表面設定温度が２５℃～９０℃の範囲にある金属ロールの間のニップを通過させることからなる、上記の太陽電池モジュール用裏面保護シートの製造方法を提供する。本発明は、更に、上記の太陽電池モジュール用裏面保護シートで発電素子を保護したことを特徴とする太陽電池モジュールを提供する。
The present invention also comprises extruding a polybutylene terephthalate resin from a flat die, and passing the extruded sheet through a nip between a rubber roll and a metal roll having a surface set temperature in the range of 25 ° C to 90 ° C. The manufacturing method of the back surface protection sheet for solar cell modules is provided. The present invention further provides a solar cell module, wherein the power generating element is protected by the above-described back surface protective sheet for solar cell module.
本発明の裏面保護シートは、外観に優れた厚物のシートであり、結果として高温高湿下に長期間暴露されても層間剥離の恐れがなく、電気絶縁性が高く、熱収縮率、水蒸気透過度が小さく、さらに封止材との溶融接着性が良好でその界面で剥離しないという効果を有する。従って、本発明の裏面保護シートを用いることにより、発電素子の劣化を引き起こすことなく長期間にわたってその特性を維持することのできる太陽電池モジュールを提供することが可能となった。
The back surface protective sheet of the present invention is a thick sheet excellent in appearance, and as a result, there is no risk of delamination even when exposed to high temperature and high humidity for a long period of time, high electrical insulation, heat shrinkage rate, water vapor It has an effect that the permeability is small, and the melt adhesiveness with the sealing material is good and it does not peel at the interface. Therefore, by using the back surface protective sheet of the present invention, it has become possible to provide a solar cell module that can maintain its characteristics over a long period of time without causing deterioration of the power generation element.
以下、本発明の裏面保護シート、その製造方法、および太陽電池モジュールについて詳細に説明する。
Hereinafter, the back surface protective sheet, the manufacturing method thereof, and the solar cell module of the present invention will be described in detail.
本発明の裏面保護シートは、接着剤で貼合することなく厚さ２００μｍ以上のシートが得られ、耐熱性を有し、封止材であるエチレン－酢酸ビニル共重合体との熱融着性が良好であるポリブチレンテレフタレート系樹脂を用いる。ポリブチレンテレフタレート系樹脂としてはポリブチレンテレフタレートのホモポリマーやその共重合体（以下、両方を併せてＰＢＴと略記する）が好ましい。また、ＰＢＴと少量のポリカーボネートやポリエチレンテレフタレートなどの熱可塑性樹脂との混合物もポリブチレンテレフタレート系樹脂として用いることができる。
The back protective sheet of the present invention provides a sheet having a thickness of 200 μm or more without being bonded with an adhesive, has heat resistance, and is heat-fusible with an ethylene-vinyl acetate copolymer as a sealing material. A polybutylene terephthalate-based resin having a good viscosity is used. The polybutylene terephthalate resin is preferably a homopolymer of polybutylene terephthalate or a copolymer thereof (hereinafter, both are abbreviated as PBT). A mixture of PBT and a small amount of a thermoplastic resin such as polycarbonate or polyethylene terephthalate can also be used as the polybutylene terephthalate resin.
ＰＢＴとしては、１，４－ブタンジオールとテレフタル酸とを重縮合させる方法、１，４－ブタンジオールとテレフタル酸の低級アルキルエステルとを重縮合させる方法などで得られるポリブチレンテレフタレートホモポリマーや、ブチレングリコールの一部をエチレングリコール、プロピレングリコール、またはシクロヘキサンジメタノールに置き換えたり、テレフタル酸の一部をイソフタル酸、２，６－ナフタレンジカルボン酸、またはアジピン酸に置き換えたりしたポリブチレンテレフタレート共重合体があり、いずれの方法で得られたＰＢＴでも用いることができる。本発明で用いられるＰＢＴの固有粘度は０．６～１．６が好ましく、さらには１．０～１．５が好ましい。ＰＢＴの固有粘度が０．６未満の場合はＰＢＴの溶融粘度が小さいために、厚さ２００μｍ以上の裏面保護シートを得ようとすると、フラットダイから押出された溶融樹脂が自重で垂れ、厚さが均一な裏面保護シートが得られないので好ましくなく、１．６を超える場合は押出し成形する際に溶融させたＰＢＴの押出し機内やフラットダイ内での流動性が悪くなるので好ましくない。
Examples of PBT include polybutylene terephthalate homopolymer obtained by polycondensation of 1,4-butanediol and terephthalic acid, polycondensation of 1,4-butanediol and lower alkyl ester of terephthalic acid, Polybutylene terephthalate copolymer in which part of butylene glycol is replaced with ethylene glycol, propylene glycol, or cyclohexanedimethanol, or part of terephthalic acid is replaced with isophthalic acid, 2,6-naphthalenedicarboxylic acid, or adipic acid PBT obtained by any method can be used. The intrinsic viscosity of the PBT used in the present invention is preferably 0.6 to 1.6, and more preferably 1.0 to 1.5. When the intrinsic viscosity of PBT is less than 0.6, the melt viscosity of PBT is small. Therefore, when trying to obtain a back protective sheet having a thickness of 200 μm or more, the molten resin extruded from the flat die drips by its own weight, and the thickness However, it is not preferable because a uniform back surface protective sheet cannot be obtained, and when it exceeds 1.6, the fluidity of the melted PBT in the extruder or in the flat die deteriorates.
太陽電池モジュールは、長期に渡って安定的に太陽エネルギーを電気エネルギーに変換することが求められており、本発明の裏面保護シートには、長期に渡ってその特性が大きく低下しないことが求められる。ＰＢＴはエステル結合を含有しており、水分により加水分解を起こして分子量が低下し、長期に渡って使用すると物性が低下する恐れがある。したがって、本発明に用いられるＰＢＴは、高温高湿下において加水分解が起こり難くい末端のカルボキシル基の数が少ないものが好ましく、具体的には、カルボキシル基当量が４０ｍｅｑ／ｋｇ以下、更に好ましくは３０ｍｅｑ／ｋｇ以下のＰＢＴが好適に使用される。
The solar cell module is required to stably convert solar energy into electric energy over a long period of time, and the back surface protection sheet of the present invention is required not to significantly deteriorate its characteristics over a long period of time. . PBT contains an ester bond, which causes hydrolysis due to moisture, resulting in a decrease in molecular weight. If used over a long period of time, the physical properties may decrease. Therefore, the PBT used in the present invention preferably has a small number of terminal carboxyl groups that hardly undergo hydrolysis under high temperature and high humidity. Specifically, the carboxyl group equivalent is 40 meq / kg or less, more preferably PBT of 30 meq / kg or less is preferably used.
本発明の裏面保護シートには、上記ＰＢＴへ加水分解を抑制するためのカルボジイミド、シート状に溶融加工する際の熱劣化を防ぐためのフェノール系、リン系、イオウ系などの酸化防止剤、太陽光に含まれる紫外線による劣化を防ぐための紫外線吸収剤や光安定剤、アンチブロッキング剤、着色剤、難燃剤などの添加剤を一種又は複数種必要に応じて添加することもできる。
The back surface protection sheet of the present invention includes carbodiimide for suppressing hydrolysis to the PBT, an antioxidant such as phenol, phosphorus, and sulfur to prevent thermal degradation during melt processing into a sheet, sun One or more additives such as an ultraviolet absorber, a light stabilizer, an antiblocking agent, a colorant, and a flame retardant for preventing deterioration due to ultraviolet rays contained in light can be added as necessary.
本発明の裏面保護シートを得るには、図１に示すように、フラットダイ１を装着した押出し機へＰＢＴを供給し、溶融したＰＢＴをフラットダイ１から吐出させ、吐出したＰＢＴを金属ロール２とゴムロール３で構成されるニップロールで引き取ることにより、外観が良好な厚みのある裏面保護シート４を得ることができる。その際、金属ロールの表面設定温度は２５℃～９０℃の範囲になるようにする。なお、後述する多層構造を有する裏面保護シートを得るには、複数の押出し機に連結したフラットダイより共押出して製造することができる。共押出は、例えば、公知のＴ－ダイ法により行うことができる。
In order to obtain the back surface protection sheet of the present invention, as shown in FIG. 1, PBT is supplied to an extruder equipped with a flat die 1, molten PBT is discharged from the flat die 1, and the discharged PBT is discharged into a metal roll 2. By taking up with a nip roll composed of the rubber roll 3, it is possible to obtain the back protective sheet 4 having a good appearance and thickness. At that time, the surface setting temperature of the metal roll is set in the range of 25 ° C. to 90 ° C. In addition, in order to obtain the back surface protection sheet which has the multilayer structure mentioned later, it can manufacture by co-extrusion from the flat die connected with the some extruder. Co-extrusion can be performed by, for example, a known T-die method.
上述のように、本発明の裏面保護シートはフラットダイから押出された溶融状態のＰＢＴを、表面設定温度が２５℃～９０℃の範囲にある金属ロールとゴムロールとでニップロール成形するのであるが、金属ロールの表面設定温度が２５℃を下回ると、厚さ２００μｍ以上の裏面保護シートを得ようとした場合、金属ロール表面で溶融した樹脂が急冷されるため、接触ムラにより金属ロールに接触した部分が冷却され結晶化し、その隣接部分に浮きが生じて、さらにＰＢＴがゴムロールへ取られる現象が生じ、平滑な裏面保護シートが得られない。一方、金属ロールの表面設定温度が９０℃を超える場合は、得られた裏面保護シートが金属ロール表面から離型し難く、引き剥がし痕と呼ばれる引取り方向（ＭＤ方向）に垂直な横筋が生じるばかりでなく、熱収縮率が大きくなるので好ましくない。このように金属ロールの表面設定温度を２５℃～９０℃の範囲とすると外観が良好な裏面保護シートが得られるのであるが、この温度範囲の中でも表面設定温度を低温側にすると、得られた裏面保護シートの熱収縮率が小さく、また、高温側にすると水蒸気透過度の小さい裏面保護シートが得られる。従って、金属ロールの表面設定温度は、これらの特性を考慮して適宜選択すると良い。
As described above, the back surface protection sheet of the present invention is a nip roll molding of a molten PBT extruded from a flat die with a metal roll and a rubber roll having a surface set temperature in the range of 25 ° C. to 90 ° C. When the surface setting temperature of the metal roll is lower than 25 ° C., the resin melted on the surface of the metal roll is rapidly cooled when trying to obtain a back surface protection sheet having a thickness of 200 μm or more. Is cooled and crystallized, and floating occurs in the adjacent portion, and further, a phenomenon that PBT is taken to the rubber roll occurs, and a smooth back surface protection sheet cannot be obtained. On the other hand, when the surface set temperature of the metal roll exceeds 90 ° C., the obtained back surface protection sheet is difficult to release from the surface of the metal roll, and horizontal stripes perpendicular to the take-off direction (MD direction) called peeling marks occur. Not only that, but also the heat shrinkage rate is increased, which is not preferable. As described above, when the surface setting temperature of the metal roll is in the range of 25 ° C. to 90 ° C., a back surface protection sheet having a good appearance can be obtained. The back surface protection sheet has a small heat shrinkage rate, and when it is on the high temperature side, a back surface protection sheet having a low water vapor permeability can be obtained. Accordingly, the surface set temperature of the metal roll may be appropriately selected in consideration of these characteristics.
また、フラットダイから押出された溶融状態のＰＢＴを、ゴムロールを用いず金属ロールのみに沿わせて成形した場合は、厚さ２００μｍ以上の裏面保護シートを得ようとすると、金属ロールの表面設定温度を２５℃～９０℃の範囲としても、金属ロールへの接触が不均一となって冷却速度が異なり平滑な裏面保護シートを得ることができない。また、フラットダイから押出された溶融状態のＰＢＴをエアチャンバーや静電ピニング等の手段を用いて強制的に金属ロールに接触させても、金属ロールへの接触が均一とはならず平滑な裏面保護シートを得ることができない。
In addition, when a molten PBT extruded from a flat die is molded along only a metal roll without using a rubber roll, a surface setting temperature of the metal roll is obtained when trying to obtain a back protective sheet having a thickness of 200 μm or more. Even when the temperature is in the range of 25 ° C. to 90 ° C., the contact with the metal roll is uneven, the cooling rate is different, and a smooth back surface protective sheet cannot be obtained. Also, even when the molten PBT extruded from the flat die is forcibly brought into contact with the metal roll using means such as an air chamber or electrostatic pinning, the contact with the metal roll is not uniform and the back surface is smooth. A protective sheet cannot be obtained.
本発明により得られたシートは、ＰＢＴを用いているために結晶化速度が速く、延伸処理しなくても実用に供し得る特性と外観を有している。そのため、製膜後に延伸するという二次加工が不要であるという効果をも有する。
The sheet obtained by the present invention uses PBT, so that the crystallization speed is high, and it has characteristics and appearance that can be put to practical use without being subjected to stretching treatment. Therefore, it also has an effect that secondary processing of stretching after film formation is unnecessary.
金属ロールとしては、クロムメッキロール、セラミック溶射ロール等のいずれを用いても良く、好ましくはサンドブラスト等の手段で表面に微細な凹凸形状を付与した後メッキ処理や溶射処理を行った金属ロールが好適に用いられる。さらには、上記金属ロール表面の温度を制御するために、温調された水やオイル等の熱媒体を循環させるための二重管構造とした金属ロールを用いるのが好ましい。
As the metal roll, any of a chrome plating roll, a ceramic sprayed roll, and the like may be used. Preferably, a metal roll subjected to a plating treatment or a thermal spraying treatment after imparting a fine uneven shape to the surface by means of sandblasting or the like is suitable. Used for. Furthermore, in order to control the temperature of the surface of the metal roll, it is preferable to use a metal roll having a double tube structure for circulating a heat medium such as water or oil whose temperature is adjusted.
ゴムロールに用いられるゴムとしては、シリコーンゴム、フッ素ゴム、ブタジエンゴム、イソプレンゴム等の合成ゴムを使用することができ、耐熱性、離型性、コストなどの観点からシリコーンゴムが好ましい。また、裏面保護シートを連続生産するとゴムロール表面の温度が上昇するので、ゴムロールもその内部へ水やオイルを循環させてゴムロールの温度を調整するのが好ましい。
As the rubber used for the rubber roll, synthetic rubber such as silicone rubber, fluorine rubber, butadiene rubber and isoprene rubber can be used, and silicone rubber is preferable from the viewpoint of heat resistance, releasability and cost. Moreover, since the temperature of a rubber roll surface will rise if a back surface protection sheet is continuously produced, it is preferable to adjust the temperature of a rubber roll also by circulating water and oil into the rubber roll.
本発明の裏面保護シートは、複数のポリブチレンテレフタレート系樹脂層からなる多層構造を有することができる。この場合、接着剤を用いることなく厚さ２００μｍ以上の多層構造が形成されるため、長期間高温高湿度下に暴露されても層間剥離の恐れがなく、電気絶縁性が高く、さらに熱収縮率が小さいという特徴があり、延伸することなくそのまま裏面保護シートとして使用することができる。
The back surface protective sheet of the present invention can have a multilayer structure composed of a plurality of polybutylene terephthalate resin layers. In this case, since a multilayer structure having a thickness of 200 μm or more is formed without using an adhesive, there is no risk of delamination even when exposed to high temperatures and high humidity for a long period of time, high electrical insulation, and thermal contraction rate Is small and can be used as it is as a back protective sheet without stretching.
本発明の裏面保護シートの厚さは２００μｍ～５００μｍとする。裏面保護シートの厚さが２００μｍ未満の場合は、電気絶縁性が低くなり（最大許容システム電圧が１０００Ｖ未満となり）、また水蒸気透過度が高くなるために水分が太陽電池モジュール内へ浸透しやすく、更に裏面保護シートの厚さが薄くコシが弱くなるため裏面保護シートを取扱い難くなるので好ましくない。一方、厚さが５００μｍを超える場合は、得られた裏面保護シートをロール状に巻き取ることが困難となり、さらにコストの面からも好ましくない。裏面保護シートの厚さは好ましくは２４０μｍ～４５０μｍである。
The thickness of the back protective sheet of the present invention is 200 μm to 500 μm. When the thickness of the back surface protective sheet is less than 200 μm, the electrical insulation is low (the maximum allowable system voltage is less than 1000 V), and the water vapor permeability is high, so that moisture easily penetrates into the solar cell module. Furthermore, since the thickness of the back surface protection sheet is thin and the stiffness is weak, it is difficult to handle the back surface protection sheet. On the other hand, when the thickness exceeds 500 μm, it is difficult to wind the obtained back surface protective sheet into a roll, which is not preferable from the viewpoint of cost. The thickness of the back protective sheet is preferably 240 μm to 450 μm.
裏面保護シートの１５０℃における熱収縮率は、引取り方向（ＭＤ方向、押出し方向と同義である）およびそれに直交する方向（即ちＴＤ方向）共に１．５％以下とし、更には１．０％以下が好ましい。１５０℃における熱収縮率が１．５％を超える場合は、太陽電池モジュールを長期間使用して裏面保護シートが収縮すると裏面保護シートと封止材との界面で内部応力が発生し、封止材との接着力が低下し、ひいては裏面保護シートが封止材より剥離するばかりでなく、太陽電池モジュールに反りが生じる、発電素子間を接続している配線が切断するなどの不具合が生じる。
The thermal shrinkage rate at 150 ° C. of the back surface protective sheet is 1.5% or less in both the take-up direction (MD direction and synonymous with the extrusion direction) and the direction orthogonal thereto (ie, TD direction), and further 1.0%. The following is preferred. When the thermal shrinkage rate at 150 ° C exceeds 1.5%, when the back surface protection sheet shrinks after using the solar cell module for a long time, internal stress is generated at the interface between the back surface protection sheet and the sealing material, and sealing As a result, the adhesive strength with the material is reduced, and not only the back surface protection sheet is peeled off from the sealing material, but also the solar cell module is warped, and the wiring connecting the power generating elements is disconnected.
また、本発明の裏面保護シートは着色剤を配合して任意の色に着色することもできる。裏面保護シートを着色する場合は、白色、または黒色に着色するのが好ましく、白色に着色する場合はＰＢＴ１００重量部に対して酸化チタンなどの白色顔料を３重量部～４０重量部、黒色に着色する場合はＰＢＴ１００重量部に対してカーボンブラックなどの黒色顔料を０．１重量部～１０重量部配合するのが好ましい。なお、裏面保護シートは白色に着色することにより、太陽エネルギーから電気エネルギーへの太陽電池モジュールの変換効率を向上させることができると共に、裏面保護シートの耐候性が向上するという効果が得られる。一方、太陽電池モジュールを屋根等に設置する場合は、デザイン的に黒色に着色した裏面保護シートが好まれる。
Also, the back surface protective sheet of the present invention can be colored in any color by blending a colorant. When coloring the back surface protective sheet, it is preferable to color white or black. When white is colored, 3 to 40 parts by weight of a white pigment such as titanium oxide is colored black to 100 parts by weight of PBT. In this case, it is preferable to add 0.1 to 10 parts by weight of a black pigment such as carbon black to 100 parts by weight of PBT. In addition, while a back surface protection sheet is colored white, while being able to improve the conversion efficiency of the solar cell module from a solar energy to an electrical energy, the effect that the weather resistance of a back surface protection sheet improves is acquired. On the other hand, when the solar cell module is installed on a roof or the like, a back protective sheet colored in black in design is preferred.
本発明の裏面保護シートは、複数のポリブチレンテレフタレート系樹脂層からなり、該複数の層の少なくとも２層は互いに異なる色を有するような多層構成とすることができる。多層構成とする場合は、全層にポリブチレンテレフタレート系樹脂を用い、共押出し法で製膜する。これにより、層間剥離が生じない裏面保護シートとすることができる。具体的には、透明層／着色層、着色層／着色層、着色層／透明層／着色層、透明層／着色層／透明層、高濃度着色層／低濃度着色層／高濃度着色層としたものなどの層構成を有する多層の裏面保護シートとしても良い。ここで、透明層とは、着色のための顔料等を含有しない層のことを示す。なお、太陽電池モジュールの外観を重視する場合は着色層を黒色に、太陽電池モジュールの発電効率を重視する場合は着色層を白色に着色するのが好ましい。また、押出し成形時にメヤニ発生の恐れがある場合は透明層／着色層／透明層の構成が好ましく、長期間使用により裏面保護シートに黄変の恐れがある場合は着色層／透明層／着色層の構成が好ましい。なお、裏面保護シートの裏面（前面版側の反対面）が黒色の場合は放熱性が向上するという効果が得られるので、前面板側の層を白色に着色し、その反対側の層を黒色に着色した多層構造の裏面保護シートが特に好適に用いられる。この場合の白色顔料と黒色顔料の使用量は上記と同様である。
The back surface protective sheet of the present invention can be composed of a plurality of polybutylene terephthalate resin layers, and at least two of the plurality of layers can have a multilayer structure having different colors. In the case of a multi-layer structure, a polybutylene terephthalate resin is used for all layers and a film is formed by a coextrusion method. Thereby, it can be set as the back surface protection sheet which does not produce delamination. Specifically, transparent layer / colored layer, colored layer / colored layer, colored layer / transparent layer / colored layer, transparent layer / colored layer / transparent layer, high-concentration colored layer / low-concentration colored layer / high-concentration colored layer It is good also as a multilayer back surface protection sheet which has layer structure, such as what was made. Here, the transparent layer refers to a layer that does not contain a pigment for coloring. In the case where importance is attached to the appearance of the solar cell module, the colored layer is preferably colored black, and in the case where importance is attached to the power generation efficiency of the solar cell module, the colored layer is preferably colored white. In addition, when there is a risk of occurrence of scratches during extrusion molding, the constitution of transparent layer / colored layer / transparent layer is preferred, and when there is a risk of yellowing the back protective sheet due to long-term use, the colored layer / transparent layer / colored layer The configuration is preferable. In addition, since the effect that heat dissipation improves when the back surface (opposite side of the front plate side) of the back surface protection sheet is black is obtained, the front plate side layer is colored white and the opposite side layer is black A back surface protective sheet having a multilayer structure colored in the above is particularly preferably used. The amount of white pigment and black pigment used in this case is the same as described above.
本発明の裏面保護シートは、特定の層を着色した多層であっても、全層にＰＢＴを用いているので、各層の線膨張係数や熱収縮率がほぼ同じであるため層間の内部応力がほとんど発生せず、層間接着性が極めてよく、高温高湿下に長期間暴露されても層間剥離が生じないという効果を有する。
Even if the back surface protective sheet of the present invention is a multilayer in which a specific layer is colored, since PBT is used for all layers, the linear expansion coefficient and thermal contraction rate of each layer are almost the same, so the internal stress between layers is Almost no generation occurs, the interlaminar adhesion is extremely good, and there is an effect that delamination does not occur even when exposed to a high temperature and high humidity for a long time.
このようにして得られた裏面保護シートを用いた太陽電池モジュールの一例を図２に示す。図２に例示した太陽電池モジュール１０は、前面板１１、封止材１３、発電素子１２、封止材１３、本発明の裏面保護シート１４からなり、この順に一体化した構造を有する。
FIG. 2 shows an example of a solar cell module using the back surface protective sheet obtained in this way. The solar cell module 10 illustrated in FIG. 2 includes a front plate 11, a sealing material 13, a power generation element 12, a sealing material 13, and a back surface protection sheet 14 of the present invention, and has a structure integrated in this order.
以下に、本発明を実施例により更に詳細に説明するが、本発明はこれらの実施例によって何ら制限されるものではない。なお、特性の評価は次の方法で行った。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. The characteristics were evaluated by the following method.
（１）固有粘度の測定
ＰＢＴをフェノール－テトラクロロエタン混合溶媒（重量比で１：１）に溶解し、ウヴェローデ型粘度計を用いて２５℃で測定することにより、固有粘度を求めた。 (1) Measurement of Intrinsic Viscosity Intrinsic viscosity was determined by dissolving PBT in a phenol-tetrachloroethane mixed solvent (1: 1 by weight) and measuring it at 25 ° C. using an Ubbelohde viscometer.
ＰＢＴをフェノール－テトラクロロエタン混合溶媒（重量比で１：１）に溶解し、ウヴェローデ型粘度計を用いて２５℃で測定することにより、固有粘度を求めた。 (1) Measurement of Intrinsic Viscosity Intrinsic viscosity was determined by dissolving PBT in a phenol-tetrachloroethane mixed solvent (1: 1 by weight) and measuring it at 25 ° C. using an Ubbelohde viscometer.
（２）最大許容システム電圧
縦１００ｍｍ、横１００ｍｍのシートに印加する電圧を徐々に上げ、部分放電が起こり始めた電圧（図３のａ：部分放電開始電圧）を１０秒間印加した後、印加電圧を下げ６０秒間電圧を印加しても放電が起こらない電圧（図３のｂ：部分放電消滅電圧）を求める。
この試験を１０個の試料について行い、部分放電消滅電圧の平均値（Ｕext）と部分放電消滅電圧の標準偏差（Ｓ）を計算し、次式により最大許容システム電圧を求めた。
最大許容システム電圧（Ｖ）＝（Ｕext－Ｓ）×１．４１４／（１．２×１．２５）
(2) Maximum allowable system voltage The voltage applied to the 100 mm long and 100 mm wide sheet is gradually increased, and the voltage at which partial discharge begins to occur (a in FIG. 3: partial discharge start voltage) is applied for 10 seconds, and then the applied voltage. The voltage at which no discharge occurs even when a voltage is applied for 60 seconds is obtained (b in FIG. 3: partial discharge extinction voltage).
This test was performed on 10 samples, the average value (Uext) of the partial discharge extinction voltage and the standard deviation (S) of the partial discharge extinction voltage were calculated, and the maximum allowable system voltage was obtained by the following equation.
Maximum allowable system voltage (V) = (Uext-S) x 1.414 / (1.2 x 1.25)
縦１００ｍｍ、横１００ｍｍのシートに印加する電圧を徐々に上げ、部分放電が起こり始めた電圧（図３のａ：部分放電開始電圧）を１０秒間印加した後、印加電圧を下げ６０秒間電圧を印加しても放電が起こらない電圧（図３のｂ：部分放電消滅電圧）を求める。
この試験を１０個の試料について行い、部分放電消滅電圧の平均値（Ｕext）と部分放電消滅電圧の標準偏差（Ｓ）を計算し、次式により最大許容システム電圧を求めた。
最大許容システム電圧（Ｖ）＝（Ｕext－Ｓ）×１．４１４／（１．２×１．２５）
(2) Maximum allowable system voltage The voltage applied to the 100 mm long and 100 mm wide sheet is gradually increased, and the voltage at which partial discharge begins to occur (a in FIG. 3: partial discharge start voltage) is applied for 10 seconds, and then the applied voltage. The voltage at which no discharge occurs even when a voltage is applied for 60 seconds is obtained (b in FIG. 3: partial discharge extinction voltage).
This test was performed on 10 samples, the average value (Uext) of the partial discharge extinction voltage and the standard deviation (S) of the partial discharge extinction voltage were calculated, and the maximum allowable system voltage was obtained by the following equation.
Maximum allowable system voltage (V) = (Uext-S) x 1.414 / (1.2 x 1.25)
（３）水蒸気透過度
水蒸気透過度は、ＡＳＴＭ Ｆ１２４９－０１の赤外線センサー法に準じ、下記の条件で測定した。
透過セルの温度：３７．８℃
高湿度セルの相対湿度：９０％（加湿窒素ガス）
低湿度セルの相対湿度：０％（乾燥窒素ガス） (3) Water vapor transmission rate The water vapor transmission rate was measured under the following conditions according to the infrared sensor method of ASTM F1249-01.
Temperature of transmission cell: 37.8 ° C
High humidity cell relative humidity: 90% (humidified nitrogen gas)
Low humidity cell relative humidity: 0% (dry nitrogen gas)
水蒸気透過度は、ＡＳＴＭ Ｆ１２４９－０１の赤外線センサー法に準じ、下記の条件で測定した。
透過セルの温度：３７．８℃
高湿度セルの相対湿度：９０％（加湿窒素ガス）
低湿度セルの相対湿度：０％（乾燥窒素ガス） (3) Water vapor transmission rate The water vapor transmission rate was measured under the following conditions according to the infrared sensor method of ASTM F1249-01.
Temperature of transmission cell: 37.8 ° C
High humidity cell relative humidity: 90% (humidified nitrogen gas)
Low humidity cell relative humidity: 0% (dry nitrogen gas)
（４）熱収縮率
縦２００ｍｍ、横２００ｍｍのシートの中央部に約１００ｍｍの間隔で標点を付け、次いで１５０℃に保持された熱風乾燥機にこの試験片を入れ、３０分間加熱した後取り出し、室温に３０分間放置してから標点間距離を測定して、次式により裏面保護シートの引取り方向（ＭＤ）およびそれに垂直な方向（ＴＤ）の熱収縮率を算出した。
熱収縮率（％）＝［（加熱前の標点間間隔－加熱後の標点間間隔）／加熱前の標点間間隔］×１００
(4) Thermal contraction rate Marks are placed at intervals of about 100 mm at the center of a sheet 200 mm long and 200 mm wide, then the test piece is placed in a hot air dryer maintained at 150 ° C., heated for 30 minutes and then removed. Then, after leaving at room temperature for 30 minutes, the distance between the gauge points was measured, and the thermal shrinkage rate in the take-up direction (MD) of the back surface protection sheet and the direction perpendicular to it (TD) was calculated by the following formula.
Thermal contraction rate (%) = [(interval between gauge points before heating−interval between gauge points after heating) / interval between gauge points before heating] × 100
縦２００ｍｍ、横２００ｍｍのシートの中央部に約１００ｍｍの間隔で標点を付け、次いで１５０℃に保持された熱風乾燥機にこの試験片を入れ、３０分間加熱した後取り出し、室温に３０分間放置してから標点間距離を測定して、次式により裏面保護シートの引取り方向（ＭＤ）およびそれに垂直な方向（ＴＤ）の熱収縮率を算出した。
熱収縮率（％）＝［（加熱前の標点間間隔－加熱後の標点間間隔）／加熱前の標点間間隔］×１００
(4) Thermal contraction rate Marks are placed at intervals of about 100 mm at the center of a sheet 200 mm long and 200 mm wide, then the test piece is placed in a hot air dryer maintained at 150 ° C., heated for 30 minutes and then removed. Then, after leaving at room temperature for 30 minutes, the distance between the gauge points was measured, and the thermal shrinkage rate in the take-up direction (MD) of the back surface protection sheet and the direction perpendicular to it (TD) was calculated by the following formula.
Thermal contraction rate (%) = [(interval between gauge points before heating−interval between gauge points after heating) / interval between gauge points before heating] × 100
［実施例１］
フラットダイを装着した三層の製膜装置を用い、両外層がポリブチレンテレフタレートホモポリマー（固有粘度：１．１、カルボキシル基当量：７ｍｅｑ／ｋｇ、以下、ＰＢＴ－Ａと略記する）、内層がＰＢＴ－Ａ１００重量部に対し酸化チタン１０重量部を配合した混合物を、それぞれの厚み比が、表層：内層：表層＝５：９０：５となるようにフラットダイより押出し、溶融状態のシートをゴムロールと表面設定温度を２５℃とした金属ロールとで挟み込んでニップロール成形することにより、厚さ２５０μｍの三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 1]
Using a three-layer film forming apparatus equipped with a flat die, both outer layers are polybutylene terephthalate homopolymer (inherent viscosity: 1.1, carboxyl group equivalent: 7 meq / kg, hereinafter abbreviated as PBT-A), A mixture in which 10 parts by weight of titanium oxide is blended with 100 parts by weight of PBT-A is extruded from a flat die so that the respective thickness ratios are surface layer: inner layer: surface layer = 5: 90: 5, and the molten sheet is rubber roll And a metal roll having a surface set temperature of 25 ° C. to form a nip roll to obtain a three-layer back protective sheet having a thickness of 250 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
フラットダイを装着した三層の製膜装置を用い、両外層がポリブチレンテレフタレートホモポリマー（固有粘度：１．１、カルボキシル基当量：７ｍｅｑ／ｋｇ、以下、ＰＢＴ－Ａと略記する）、内層がＰＢＴ－Ａ１００重量部に対し酸化チタン１０重量部を配合した混合物を、それぞれの厚み比が、表層：内層：表層＝５：９０：５となるようにフラットダイより押出し、溶融状態のシートをゴムロールと表面設定温度を２５℃とした金属ロールとで挟み込んでニップロール成形することにより、厚さ２５０μｍの三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 1]
Using a three-layer film forming apparatus equipped with a flat die, both outer layers are polybutylene terephthalate homopolymer (inherent viscosity: 1.1, carboxyl group equivalent: 7 meq / kg, hereinafter abbreviated as PBT-A), A mixture in which 10 parts by weight of titanium oxide is blended with 100 parts by weight of PBT-A is extruded from a flat die so that the respective thickness ratios are surface layer: inner layer: surface layer = 5: 90: 5, and the molten sheet is rubber roll And a metal roll having a surface set temperature of 25 ° C. to form a nip roll to obtain a three-layer back protective sheet having a thickness of 250 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
［実施例２］
厚さを３００μｍとした以外は実施例１と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 2]
A three-layer back protective sheet was obtained in the same manner as in Example 1 except that the thickness was 300 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
厚さを３００μｍとした以外は実施例１と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 2]
A three-layer back protective sheet was obtained in the same manner as in Example 1 except that the thickness was 300 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
［実施例３～５］
フラットダイを装着した三層の製膜装置を用い、両外層がＰＢＴ－Ａ１００重量部に対し酸化チタン２０重量部を配合した混合物、内層がＰＢＴ－Ａ１００重量部に対し酸化チタン１０重量部を配合した混合物を、それぞれの厚み比が、表層：内層：表層＝５：９０：５となるようにフラットダイより押出し、溶融状態のシートをゴムロールと金属ロールとで挟み込んでニップロール成形することにより、三層の裏面保護シートを得た。金属ロールの表面設定温度、得られた裏面保護シートの外観、厚さ、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Examples 3 to 5]
Using a three-layer film-forming device equipped with a flat die, both outer layers are blended with 20 parts by weight of titanium oxide per 100 parts by weight of PBT-A, and the inner layer is blended with 10 parts by weight of titanium oxide per 100 parts by weight of PBT-A. The resulting mixture was extruded from a flat die so that the respective thickness ratios were surface layer: inner layer: surface layer = 5: 90: 5, and the melted sheet was sandwiched between a rubber roll and a metal roll to form a nip roll. A back protective sheet for the layer was obtained. Table 1 shows the surface set temperature of the metal roll, the appearance, thickness, maximum allowable system voltage, water vapor permeability, and heat shrinkage rate of the obtained back surface protective sheet.
フラットダイを装着した三層の製膜装置を用い、両外層がＰＢＴ－Ａ１００重量部に対し酸化チタン２０重量部を配合した混合物、内層がＰＢＴ－Ａ１００重量部に対し酸化チタン１０重量部を配合した混合物を、それぞれの厚み比が、表層：内層：表層＝５：９０：５となるようにフラットダイより押出し、溶融状態のシートをゴムロールと金属ロールとで挟み込んでニップロール成形することにより、三層の裏面保護シートを得た。金属ロールの表面設定温度、得られた裏面保護シートの外観、厚さ、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Examples 3 to 5]
Using a three-layer film-forming device equipped with a flat die, both outer layers are blended with 20 parts by weight of titanium oxide per 100 parts by weight of PBT-A, and the inner layer is blended with 10 parts by weight of titanium oxide per 100 parts by weight of PBT-A. The resulting mixture was extruded from a flat die so that the respective thickness ratios were surface layer: inner layer: surface layer = 5: 90: 5, and the melted sheet was sandwiched between a rubber roll and a metal roll to form a nip roll. A back protective sheet for the layer was obtained. Table 1 shows the surface set temperature of the metal roll, the appearance, thickness, maximum allowable system voltage, water vapor permeability, and heat shrinkage rate of the obtained back surface protective sheet.
［実施例６］
内層としてＰＢＴ－Ａ１００重量部に対しカーボンブラック０．３重量部を配合した混合物を用いた以外は実施例１と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 6]
A three-layer back protective sheet was obtained in the same manner as in Example 1 except that a mixture of 0.3 parts by weight of carbon black with 100 parts by weight of PBT-A was used as the inner layer. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
内層としてＰＢＴ－Ａ１００重量部に対しカーボンブラック０．３重量部を配合した混合物を用いた以外は実施例１と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Example 6]
A three-layer back protective sheet was obtained in the same manner as in Example 1 except that a mixture of 0.3 parts by weight of carbon black with 100 parts by weight of PBT-A was used as the inner layer. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
［比較例１］
全体の厚さを１８８μｍとした以外は実施例４と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Comparative Example 1]
A three-layer back protective sheet was obtained in the same manner as in Example 4 except that the total thickness was 188 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
全体の厚さを１８８μｍとした以外は実施例４と同様にして、三層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Comparative Example 1]
A three-layer back protective sheet was obtained in the same manner as in Example 4 except that the total thickness was 188 μm. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
［比較例２］
フラットダイを装着した三層の製膜装置を用い、全層にＰＢＴ－Ａを供給してフラットダイより押出し、溶融状態のシートをゴムロールと表面設定温度を７０℃とした金属ロールとで挟み込んでニップロール成形することにより、厚さ１８８μｍの単層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Comparative Example 2]
Using a three-layer film forming apparatus equipped with a flat die, PBT-A is supplied to all layers and extruded from the flat die, and the molten sheet is sandwiched between a rubber roll and a metal roll having a surface set temperature of 70 ° C. By performing nip roll molding, a single-layer back protective sheet having a thickness of 188 μm was obtained. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
フラットダイを装着した三層の製膜装置を用い、全層にＰＢＴ－Ａを供給してフラットダイより押出し、溶融状態のシートをゴムロールと表面設定温度を７０℃とした金属ロールとで挟み込んでニップロール成形することにより、厚さ１８８μｍの単層の裏面保護シートを得た。得られた裏面保護シートの外観、最大許容システム電圧、水蒸気透過度、熱収縮率を表１に示す。 [Comparative Example 2]
Using a three-layer film forming apparatus equipped with a flat die, PBT-A is supplied to all layers and extruded from the flat die, and the molten sheet is sandwiched between a rubber roll and a metal roll having a surface set temperature of 70 ° C. By performing nip roll molding, a single-layer back protective sheet having a thickness of 188 μm was obtained. Table 1 shows the appearance, maximum allowable system voltage, water vapor transmission rate, and heat shrinkage rate of the obtained back surface protection sheet.
［比較例３］
金属ロールの表面設定温度を２０℃とした以外は比較例１と同様にし、厚さを２５０μｍの三層の裏面保護シートを得た。得られた裏面保護シートは、ニップロール成形時、急冷されたためシート端部に浮きが生じ、またゴムロールとの離型性が悪く部分的にゴムロールに取られ、全体が平滑でなく、外観が著しく不良であった。 [Comparative Example 3]
A three-layer back protective sheet having a thickness of 250 μm was obtained in the same manner as in Comparative Example 1 except that the surface setting temperature of the metal roll was 20 ° C. The resulting back surface protection sheet was rapidly cooled during nip roll forming, so that the sheet edge floated, the releasability from the rubber roll was poor, and it was partially taken up by the rubber roll. Met.
金属ロールの表面設定温度を２０℃とした以外は比較例１と同様にし、厚さを２５０μｍの三層の裏面保護シートを得た。得られた裏面保護シートは、ニップロール成形時、急冷されたためシート端部に浮きが生じ、またゴムロールとの離型性が悪く部分的にゴムロールに取られ、全体が平滑でなく、外観が著しく不良であった。 [Comparative Example 3]
A three-layer back protective sheet having a thickness of 250 μm was obtained in the same manner as in Comparative Example 1 except that the surface setting temperature of the metal roll was 20 ° C. The resulting back surface protection sheet was rapidly cooled during nip roll forming, so that the sheet edge floated, the releasability from the rubber roll was poor, and it was partially taken up by the rubber roll. Met.
［比較例４］
金属ロールの表面設定温度を１００℃とした以外は比較例２と同様にし、厚さを２５０μｍの単層の裏面保護シートを得た。得られた裏面保護シートは、金属ロールから剥離される際、金属ロールとの剥離性が悪く金属ロールに取られ引き剥がし筋が付き、全体が平滑でなく、外観が不良であった。 [Comparative Example 4]
A single-layer back surface protective sheet having a thickness of 250 μm was obtained in the same manner as in Comparative Example 2 except that the surface setting temperature of the metal roll was set to 100 ° C. When the obtained back surface protective sheet was peeled off from the metal roll, the peelability from the metal roll was poor, and it was taken off by the metal roll and had peeling lines, the entire surface was not smooth, and the appearance was poor.
金属ロールの表面設定温度を１００℃とした以外は比較例２と同様にし、厚さを２５０μｍの単層の裏面保護シートを得た。得られた裏面保護シートは、金属ロールから剥離される際、金属ロールとの剥離性が悪く金属ロールに取られ引き剥がし筋が付き、全体が平滑でなく、外観が不良であった。 [Comparative Example 4]
A single-layer back surface protective sheet having a thickness of 250 μm was obtained in the same manner as in Comparative Example 2 except that the surface setting temperature of the metal roll was set to 100 ° C. When the obtained back surface protective sheet was peeled off from the metal roll, the peelability from the metal roll was poor, and it was taken off by the metal roll and had peeling lines, the entire surface was not smooth, and the appearance was poor.
以上の結果から明らかなように、表面設定温度を２５℃～９０℃に制御した金属ロールを用いてニップロール成形された実施例１～６の裏面保護シートは外観が良好であったが、金属ロールの表面設定温度が２０℃と低い場合は、得られた裏面保護シートの端部が波打ち、平滑な裏面保護シートが得られず、また、金属ロールの表面設定温度が１００℃と高すぎる場合は、裏面保護シートを金属ロールより引き剥がす際、金属ロールとの剥離性が悪く引き剥がし筋が発生し外観が不良であった。一方、厚さを２００μｍ以上とした実施例１～６で得られた裏面保護シートの最大許容システム電圧はいずれも１０００Ｖ以上で電気絶縁性が良好であったが、厚さを１８８μｍとした比較例１および２で得られた裏面保護シートの最大許容システム電圧は１０００Ｖ未満で電気絶縁性が悪く、裏面保護シートに要求される値に達しなかった。さらに、実施例１～６で得られた裏面保護シートは、ＰＢＴを延伸することなく成形しているため、その熱収縮率はいずれも１％未満であり、太陽電池モジュールとした場合に長期に渡って屋外に暴露されても裏面保護シート自身の層間剥離がなく内部応力も抑えられ、封止材との剥離の恐れが少ないものであった。
As is apparent from the above results, the back surface protective sheets of Examples 1 to 6 formed by nip roll molding using a metal roll whose surface set temperature was controlled to 25 ° C. to 90 ° C. had good appearance. When the surface set temperature is as low as 20 ° C, the end portion of the obtained back surface protection sheet is wavy, a smooth back surface protection sheet cannot be obtained, and when the surface set temperature of the metal roll is too high as 100 ° C When the back protective sheet was peeled off from the metal roll, the peelability from the metal roll was poor, and stripping lines were generated, resulting in poor appearance. On the other hand, the maximum allowable system voltage of the backside protection sheets obtained in Examples 1 to 6 having a thickness of 200 μm or more was 1000 V or more, and the electrical insulation was good, but the thickness was 188 μm. The maximum permissible system voltage of the backside protective sheet obtained in 1 and 2 was less than 1000 V and the electrical insulation was poor, and did not reach the value required for the backside protective sheet. Furthermore, since the back surface protection sheets obtained in Examples 1 to 6 were formed without stretching PBT, their thermal shrinkage rates were all less than 1%, and long-term when a solar cell module was obtained. Even when exposed to the outdoors, there was no delamination of the back protective sheet itself, the internal stress was suppressed, and there was little risk of peeling from the sealing material.
As is apparent from the above results, the back surface protective sheets of Examples 1 to 6 formed by nip roll molding using a metal roll whose surface set temperature was controlled to 25 ° C. to 90 ° C. had good appearance. When the surface set temperature is as low as 20 ° C, the end portion of the obtained back surface protection sheet is wavy, a smooth back surface protection sheet cannot be obtained, and when the surface set temperature of the metal roll is too high as 100 ° C When the back protective sheet was peeled off from the metal roll, the peelability from the metal roll was poor, and stripping lines were generated, resulting in poor appearance. On the other hand, the maximum allowable system voltage of the backside protection sheets obtained in Examples 1 to 6 having a thickness of 200 μm or more was 1000 V or more, and the electrical insulation was good, but the thickness was 188 μm. The maximum permissible system voltage of the backside protective sheet obtained in 1 and 2 was less than 1000 V and the electrical insulation was poor, and did not reach the value required for the backside protective sheet. Furthermore, since the back surface protection sheets obtained in Examples 1 to 6 were formed without stretching PBT, their thermal shrinkage rates were all less than 1%, and long-term when a solar cell module was obtained. Even when exposed to the outdoors, there was no delamination of the back protective sheet itself, the internal stress was suppressed, and there was little risk of peeling from the sealing material.
１：フラットダイ
２：金属ロール
３：ゴムロール
４：裏面保護シート
１０：太陽電池モジュール
１１：前面板
１２：発電素子
１３：封止材
１４：裏面保護シート
ａ：部分放電開始電圧
ｂ：部分放電消滅電圧
1: Flat die 2: Metal roll 3: Rubber roll 4: Back surface protection sheet 10: Solar cell module 11: Front panel 12: Power generation element 13: Sealing material 14: Back surface protection sheet a: Partial discharge start voltage b: Partial discharge disappearance Voltage
２：金属ロール
３：ゴムロール
４：裏面保護シート
１０：太陽電池モジュール
１１：前面板
１２：発電素子
１３：封止材
１４：裏面保護シート
ａ：部分放電開始電圧
ｂ：部分放電消滅電圧
1: Flat die 2: Metal roll 3: Rubber roll 4: Back surface protection sheet 10: Solar cell module 11: Front panel 12: Power generation element 13: Sealing material 14: Back surface protection sheet a: Partial discharge start voltage b: Partial discharge disappearance Voltage
Claims (9)
- ポリブチレンテレフタレート系樹脂からなり、無延伸であるとともに、厚さが２００μｍ～５００μｍであり、且つ１５０℃における熱収縮率が引取り方向およびそれに直交する方向共に１．５％以下であることを特徴とする太陽電池モジュール用裏面保護シート。
It is made of polybutylene terephthalate resin, is unstretched, has a thickness of 200 μm to 500 μm, and has a heat shrinkage rate at 150 ° C. of 1.5% or less in both the take-up direction and the direction perpendicular thereto. The back surface protection sheet for solar cell modules.
- 前記ポリブチレンテレフタレート系樹脂の固有粘度が１．０～１．５であることを特徴とする請求項１に記載の太陽電池モジュール用裏面保護シート。
The back protective sheet for a solar cell module according to claim 1, wherein the polybutylene terephthalate resin has an intrinsic viscosity of 1.0 to 1.5.
- 前記裏面保護シートは複数のポリブチレンテレフタレート系樹脂層からなり、該複数の層の少なくとも２層は互いに異なる色を有することを特徴とする請求項１に記載の太陽電池モジュール用裏面保護シート。
The said back surface protection sheet consists of a some polybutylene terephthalate type resin layer, At least 2 layer of this layer has a mutually different color, The back surface protection sheet for solar cell modules of Claim 1 characterized by the above-mentioned.
- 前記複数の層の少なくとも一層が白色又は黒色に着色されていることを特徴とする請求項３に記載の太陽電池モジュール用裏面保護シート。
The back surface protective sheet for a solar cell module according to claim 3, wherein at least one of the plurality of layers is colored white or black.
- 前記複数の層の少なくとも一層が白色に着色され、残りの層の少なくとも一層が黒色に着色されていることを特徴とする請求項３に記載の太陽電池モジュール用裏面保護シート。
The back surface protective sheet for a solar cell module according to claim 3, wherein at least one of the plurality of layers is colored white and at least one of the remaining layers is colored black.
- 前記裏面保護シートは、前記ポリブチレンテレフタレート系樹脂をフラットダイより押出し、押出したシートをゴムロールと表面設定温度が２５℃～９０℃の範囲にある金属ロールとの間のニップを通過させることにより得られたものである、請求項１乃至５のいずれかに記載の太陽電池モジュール用裏面保護シート。
The back surface protective sheet is obtained by extruding the polybutylene terephthalate resin from a flat die and passing the extruded sheet through a nip between a rubber roll and a metal roll having a surface set temperature in the range of 25 ° C to 90 ° C. The back surface protection sheet for solar cell modules in any one of Claims 1 thru | or 5 which was made.
- ポリブチレンテレフタレート系樹脂をフラットダイより押出し、押出したシートをゴムロールと表面設定温度が２５℃～９０℃の範囲にある金属ロールの間のニップを通過させることからなる、請求項１に記載の太陽電池モジュール用裏面保護シートの製造方法。
2. The solar cell according to claim 1, wherein the polybutylene terephthalate resin is extruded from a flat die, and the extruded sheet is passed through a nip between a rubber roll and a metal roll having a surface set temperature in the range of 25 ° C. to 90 ° C. The manufacturing method of the back surface protection sheet for battery modules.
- 前記ゴムロールがシリコーンゴムロールであることを特徴とする請求項７に記載の太陽電池モジュール用裏面保護シート。
The said rubber roll is a silicone rubber roll, The back surface protection sheet for solar cell modules of Claim 7 characterized by the above-mentioned.
- 請求項１に記載の太陽電池モジュール用裏面保護シートで発電素子を保護したことを特徴とする太陽電池モジュール。
A solar cell module, wherein the power generation element is protected by the back surface protection sheet for a solar cell module according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-291860 | 2010-12-28 | ||
| JP2010291860 | 2010-12-28 |
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| Publication Number | Publication Date |
|---|---|
| WO2012091004A1 true WO2012091004A1 (en) | 2012-07-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/080197 WO2012091004A1 (en) | 2010-12-28 | 2011-12-27 | Protective sheet for back surface of solar cell modules, production method for protective sheet, and solar cell module |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW201242052A (en) |
| WO (1) | WO2012091004A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014080806A1 (en) * | 2012-11-22 | 2014-05-30 | 日東電工株式会社 | Surface protection sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007129204A (en) * | 2005-10-07 | 2007-05-24 | Toray Ind Inc | Film for sealing rear surface of solar cell, and solar cell using the same |
| WO2010018662A1 (en) * | 2008-08-12 | 2010-02-18 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin mixture and film |
-
2011
- 2011-12-26 TW TW100148613A patent/TW201242052A/en unknown
- 2011-12-27 WO PCT/JP2011/080197 patent/WO2012091004A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007129204A (en) * | 2005-10-07 | 2007-05-24 | Toray Ind Inc | Film for sealing rear surface of solar cell, and solar cell using the same |
| WO2010018662A1 (en) * | 2008-08-12 | 2010-02-18 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin mixture and film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014080806A1 (en) * | 2012-11-22 | 2014-05-30 | 日東電工株式会社 | Surface protection sheet |
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| TW201242052A (en) | 2012-10-16 |
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