JP5209568B2 - White polyester film for solar cell back surface protection sheet - Google Patents
White polyester film for solar cell back surface protection sheet Download PDFInfo
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- JP5209568B2 JP5209568B2 JP2009105059A JP2009105059A JP5209568B2 JP 5209568 B2 JP5209568 B2 JP 5209568B2 JP 2009105059 A JP2009105059 A JP 2009105059A JP 2009105059 A JP2009105059 A JP 2009105059A JP 5209568 B2 JP5209568 B2 JP 5209568B2
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- back surface
- cell back
- white polyester
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- 229920006267 polyester film Polymers 0.000 title claims description 31
- 230000004224 protection Effects 0.000 title claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 33
- 230000032798 delamination Effects 0.000 claims description 32
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 28
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 28
- -1 polyethylene terephthalate Polymers 0.000 claims description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 230000001681 protective effect Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 56
- 238000000034 method Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Photovoltaic Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、太陽電池裏面保護シート用白色ポリエステルフィルムに関する。 The present invention relates to a white polyester film for a solar cell back surface protective sheet.
次世代のエネルギー源としてクリーンエネルギーである太陽電池が注目を浴びている。太陽電池モジュールの構成は、光入射側から順に、ガラス等の高光線透過材／樹脂封止材／太陽電池セル／樹脂封止材／裏面保護シートを基本とするものである。裏面保護シートは、太陽電池セルの固定、保護、電気絶縁の目的に用いられるもので、複数のフィルム、シートが積層された構成とするのが一般的である。代表的な構成としては、白色ポリエステルフィルム／無機酸化物薄膜層／白色ポリエステルフィルムを積層した構成などが開示されている。用いられる白色ポリエステルフィルムには、耐加水分解性、隠蔽性、光線反射性、耐ＵＶ性、電気絶縁性などが求められている。 Solar cells, which are clean energy, are attracting attention as the next-generation energy source. The configuration of the solar cell module is based on a high light-transmitting material such as glass / resin encapsulant / solar cell / resin encapsulant / back surface protective sheet in order from the light incident side. The back surface protection sheet is used for the purpose of fixing, protecting, and electrically insulating solar cells, and generally has a structure in which a plurality of films and sheets are laminated. As a typical configuration, a configuration in which a white polyester film / inorganic oxide thin film layer / white polyester film is laminated is disclosed. The white polyester film used is required to have hydrolysis resistance, concealment, light reflectivity, UV resistance, electrical insulation and the like.
太陽電池は屋外で使用されることが多く、気温の日中変動や季節変動に伴う熱膨張、収縮により、裏面保護シート内の積層フィルム間、裏面保護シートと封止材間での界面剥離やフィルム内部でのデラミネーションが起こることが問題となっている。フィルム内部でデラミネーションが起こると、裏面保護シートの保護性能が低下し、水分が浸透して太陽電池セルの部分に劣化が起こる。さらに、裏面保護シート上には太陽電池モジュールから電力を取り出すための中継ボックスが取り付けられるが、屋外で風雨にさらされた場合、フィルムが劣化して内部にデラミネーションが起こり、中継ボックスが脱落することがある。従って、上記のデラミネーション強度は、高温、高湿環境下での劣化試験後もある値を維持することが必要である。近年では、耐加水分解性や耐ＵＶ性などよりもむしろ、ポリエステルフィルムの耐デラミネーション性の方が重視される傾向にある。それは、加水分解やＵＶ光による劣化が進行しても直ちにフィルム破壊につながる訳ではないが、フィルム内にデラミネーションが発生してしまうと直ちに太陽電池セルに水分などの影響が及び、太陽電池モジュールの発電性能が低下してしまうためである。従来から開示されているポリエステルフィルムには、耐デラミネーション性に対して十分な考慮がされていなかった。 Solar cells are often used outdoors, and due to thermal expansion and contraction due to daytime and seasonal fluctuations in temperature, interfacial delamination between laminated films in the back protection sheet and between the back protection sheet and the sealing material The problem is that delamination occurs inside the film. When delamination occurs inside the film, the protection performance of the back surface protection sheet decreases, moisture penetrates, and deterioration occurs in the solar battery cell portion. In addition, a relay box for extracting power from the solar cell module is mounted on the back surface protection sheet. However, when exposed to wind and rain outdoors, the film deteriorates and delamination occurs inside, causing the relay box to drop off. Sometimes. Therefore, it is necessary to maintain the delamination strength at a certain value even after a deterioration test under a high temperature and high humidity environment. In recent years, there is a tendency that delamination resistance of a polyester film is more important than hydrolysis resistance or UV resistance. It does not immediately lead to film destruction even if degradation due to hydrolysis or UV light progresses. However, if delamination occurs in the film, it immediately affects the solar cells, and the solar cell module. This is because the power generation performance is reduced. Conventionally disclosed polyester films have not been sufficiently considered for delamination resistance.
本発明は、十分な隠蔽性を備え、フィルム内部でのデラミネーション強度が高く、安定して製膜することができる太陽電池裏面保護シート用白色ポリエステルフィルムを提供することを課題とする。 This invention makes it a subject to provide the white polyester film for solar cell back surface protection sheets which has sufficient concealability, the delamination intensity | strength inside a film is high, and can form into a film stably.
すなわち本発明は、酸化チタン粒子を７〜１３重量％含有するポリエチレンテレフタレート組成物からなる白色ポリエステルフィルムであり、フィルムのポリエチレンテレフタレートの数平均分子量が１２０００〜１７０００であり、フィルムの初期デラミネーション強度が６Ｎ／１５ｍｍ以上であることを特徴とする、太陽電池裏面保護シート用白色ポリエステルフィルムである。 That is, the present invention is a white polyester film comprising a polyethylene terephthalate composition containing 7 to 13% by weight of titanium oxide particles, the number average molecular weight of the polyethylene terephthalate of the film is 12000 to 17000, and the initial delamination strength of the film is It is 6N / 15mm or more, It is a white polyester film for solar cell back surface protection sheets.
本発明によれば、十分な隠蔽性を備え、フィルム内部でのデラミネーション強度が高く、安定して製膜することができる太陽電池裏面保護シート用白色ポリエステルフィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the white polyester film for solar cell back surface protection sheets which has sufficient concealment property, has high delamination intensity | strength inside a film, and can form into a film stably can be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
［ポリエチレンテレフタレート］
本発明の太陽電池裏面保護シート用白色ポリエステルフィルムは、酸化チタン粒子を７〜１３重量％含有するポリエチレンテレフタレート組成物からなる。
ポリエチレンテレフタレートは、ホモポリマーであってもコポリマーであってもよい。コポリマーである場合、共重合成分としては、例えばイソフタル酸、ナフタレンジカルボン酸を用いることができる。コポリマーである場合の共重合成分の含有量は、例えば２０モル％以下、好ましくは１０モル％以下である。
[polyethylene terephthalate]
The white polyester film for solar cell back surface protection sheet of this invention consists of a polyethylene terephthalate composition which contains 7-13 weight% of titanium oxide particles.
The polyethylene terephthalate may be a homopolymer or a copolymer. In the case of a copolymer, for example, isophthalic acid or naphthalenedicarboxylic acid can be used as a copolymerization component. The content of the copolymer component in the case of a copolymer is, for example, 20 mol% or less, preferably 10 mol% or less.
本発明においてはフィルムのポリエチレンテレフタレートの数平均分子量は１２０００〜１７０００であることが肝要である。数平均分子量が１２０００未満であるとフィルム製膜の延伸工程で破断が発生し易く、安定した生産を行うことができない。他方、１７０００を超えるものは太陽電池裏面保護シートして用いたときにフィルムがデラミネーションを起こしやすい。このポリエチレンテレフタレートの数平均分子量は、耐候試験後のデラミネーション強度のさらに高いフィルムを得る観点から１４０００〜１７０００であることが好ましい。 In the present invention, it is important that the number average molecular weight of polyethylene terephthalate of the film is 12000 to 17000. When the number average molecular weight is less than 12,000, breakage is likely to occur in the stretching process of film formation, and stable production cannot be performed. On the other hand, a film exceeding 17000 tends to cause delamination when used as a solar cell back surface protective sheet. The number average molecular weight of the polyethylene terephthalate is preferably 14000 to 17000 from the viewpoint of obtaining a film having higher delamination strength after the weather resistance test.
フィルムのポリエチレンテレフタレートの数平均分子量をこの範囲とするためには、フィルム製造原料のポリエチレンテレフタレートとして、固有粘度が０．５０〜０．５８のポリエチレンテレフタレートを用いることが好ましい。この範囲の固有粘度のポリエチレンテレフタレートを用い、さらに適切な乾燥、溶融押出し条件をとることで、太陽電池裏面保護シートとして使用したときにデラミネーションの発生することのないフィルムを良好な押出性と生産性で得ることができる。 In order to make the number average molecular weight of the polyethylene terephthalate of the film within this range, it is preferable to use polyethylene terephthalate having an intrinsic viscosity of 0.50 to 0.58 as the polyethylene terephthalate of the film production raw material. By using polyethylene terephthalate with an intrinsic viscosity in this range, and taking appropriate drying and melt extrusion conditions, a film that does not cause delamination when used as a solar cell back surface protection sheet is produced and produced. Can be obtained by sex.
［酸化チタン粒子］
酸化チタン自体の結晶形態にはルチル型とアナターゼ型があるが、本発明では、ルチル型酸化チタン、アナターゼ型酸化チタンのいずれも用いることができ、好ましくはアナターゼ型酸化チタンの粒子を用いる。
[Titanium oxide particles]
There are rutile type and anatase type crystal forms of titanium oxide itself. In the present invention, either rutile type titanium oxide or anatase type titanium oxide can be used, and preferably anatase type titanium oxide particles are used.
酸化チタン粒子の平均粒径は、好ましくは０．１〜５．０μｍ、特に好ましくは０．１〜３．０μｍである。この範囲の平均粒径の酸化チタン粒子を用いることで、良好な分散性で酸化チタン粒子をポリエチレンテレフタレート中に分散させることができ、粒子の凝集が起こらないため均一なフィルムを得ることができるともに、良好な延伸性でフィルムを製膜することができる。 The average particle diameter of the titanium oxide particles is preferably 0.1 to 5.0 μm, particularly preferably 0.1 to 3.0 μm. By using titanium oxide particles having an average particle diameter in this range, the titanium oxide particles can be dispersed in polyethylene terephthalate with good dispersibility, and a uniform film can be obtained because the particles do not aggregate. A film can be formed with good stretchability.
酸化チタン粒子をポリエチレンテレフタレート中に分散含有させ、酸化チタン粒子を含有するポリエチレンテレフタレート組成物にする方法として、従来より公知の各種の方法を用いることができる。その代表的な方法として、下記の方法を挙げることができる。
（ア）ポリエチレンテレフタレート合成時のエステル交換反応もしくはエステル化反応終了前に、酸化チタン粒子を添加もしくは重縮合反応開始前に添加する方法。
（イ）ポリエチレンテレフタレートに酸化チタン粒子を添加し、溶融混練する方法。
（ウ）上記（ア）、（イ）の方法において酸化チタン粒子を多量添加したペレットを製造し、これらと酸化チタン粒子を含有しないポリエチレンテレフタレートのペレットとを混練して所定量の酸化チタン粒子を含有させる方法。
（エ）上記（ウ）のペレットをそのまま使用する方法。
Various conventionally known methods can be used as a method of dispersing titanium oxide particles in polyethylene terephthalate to obtain a polyethylene terephthalate composition containing titanium oxide particles. The following method can be mentioned as the typical method.
(A) A method in which titanium oxide particles are added or added before the start of polycondensation reaction before the end of the transesterification or esterification reaction during the synthesis of polyethylene terephthalate.
(A) A method in which titanium oxide particles are added to polyethylene terephthalate and melt kneaded.
(C) Producing pellets with a large amount of titanium oxide particles added in the methods (a) and (b) above, and kneading these with polyethylene terephthalate pellets not containing titanium oxide particles to produce a predetermined amount of titanium oxide particles. Method of inclusion.
(D) A method of using the pellets of (c) as it is.
本発明のポリエチレンテレフタレート組成物は、組成物１００重量％あたり酸化チタン粒子を７〜１３重量％、好ましくは７〜１０％含有する。７重量％未満であるとフィルムに十分な隠蔽性を付与することができない。他方、１３重量％を超えると、太陽電池裏面保護シートして用いたときにフィルムがデラミネーションを起こしやすい。 The polyethylene terephthalate composition of the present invention contains 7 to 13% by weight, preferably 7 to 10%, of titanium oxide particles per 100% by weight of the composition. If it is less than 7% by weight, sufficient concealability cannot be imparted to the film. On the other hand, if it exceeds 13% by weight, the film tends to cause delamination when used as a solar cell back surface protective sheet.
本発明の太陽電池裏面保護シート用ポリエステルフィルムは、初期デラミネーション強度が６Ｎ／１５ｍｍ以上、好ましくは８Ｎ／１５ｍｍ以上である。初期デラミネーション強度が６Ｎ／１５ｍｍ未満であると、太陽電池裏面保護シート用ポリエステルフィルムとして必要十分なフィルム内部でのデラミネーション強度を得ることができない。 The polyester film for a solar cell back surface protective sheet of the present invention has an initial delamination strength of 6 N / 15 mm or more, preferably 8 N / 15 mm or more. When the initial delamination strength is less than 6 N / 15 mm, the delamination strength inside the film that is necessary and sufficient as the polyester film for the solar cell back surface protection sheet cannot be obtained.
本発明の太陽電池裏面保護シート用ポリエステルフィルムは、８５℃・８５％ＲＨの雰囲気にフィルムを１０００時間エージングした後のデラミネーション強度が、好ましくは４Ｎ／１５ｍｍ以上、さらに好ましくは６Ｎ／ｍｍ以上である。このデラミネーション強度が４Ｎ／１５ｍｍ以上であることで、太陽電池裏面保護シートとして屋外で長期間使用したときにもデラミネーションの発生することのない太陽電池裏面保護シート用白色ポリエステルフィルムを得ることができる。 The polyester film for a solar cell back surface protective sheet of the present invention has a delamination strength of preferably 4 N / 15 mm or more, more preferably 6 N / mm or more after aging the film in an atmosphere of 85 ° C. and 85% RH for 1000 hours. is there. When the delamination strength is 4 N / 15 mm or more, it is possible to obtain a white polyester film for a solar cell back surface protection sheet that does not cause delamination even when used outdoors for a long time as a solar cell back surface protection sheet. it can.
［厚み］
本発明の太陽電池裏面保護シート用白色ポリエステルフィルムの厚みは、好ましくは２０〜３５０μｍ、さらに好ましくは４０〜２５０μｍ、特に好ましくは５０〜２００μｍである。この範囲の厚みであることで、太陽電池裏面保護シートとして用いたときに十分な隠蔽性を得ることができる。３５０μｍを超える厚みとしてもそれ以上の隠蔽性の上昇は望めない。
[Thickness]
The thickness of the white polyester film for solar cell back surface protective sheet of the present invention is preferably 20 to 350 μm, more preferably 40 to 250 μm, and particularly preferably 50 to 200 μm. When the thickness is within this range, sufficient concealability can be obtained when used as a solar cell back surface protective sheet. Even if the thickness exceeds 350 μm, no further increase in concealability can be expected.
［太陽電池裏面保護シート］
本発明の太陽電池裏面保護シート用白色ポリエステルフィルムは、そのうえに耐候性フィルムを貼り合わせ、太陽電池裏面保護シートとすることができる。耐光性フィルムは片面に貼り合わせてもよく、両面に貼り合わせてもよい。いずれの場合も、耐候性フィルムが、太陽電池モジュールの最外層になるようにして用いることが好ましい。
[Solar cell back surface protection sheet]
The white polyester film for a solar cell back surface protective sheet of the present invention can be used as a solar cell back surface protective sheet by laminating a weather resistant film thereon. The light-resistant film may be bonded to one side or may be bonded to both sides. In any case, it is preferable to use the weather resistant film so that it is the outermost layer of the solar cell module.
［製造方法］
本発明の太陽電池裏面保護膜用白色ポリエステルフィルムは、固有粘度０．５０〜０．５８のポリエチレンテレフタレートおよび酸化チタン粒子を原料として用いて製造することができる。具体的には、例えば以下のようにすればよい。
[Production method]
The white polyester film for a solar cell back surface protective film of the present invention can be produced using polyethylene terephthalate having an intrinsic viscosity of 0.50 to 0.58 and titanium oxide particles as raw materials. Specifically, for example, the following may be performed.
固有粘度０．５０〜０．５８のポリエチレンテレフタレートと酸化チタン粒子を押出機によって溶融押出し、必要に応じてフィルタによって溶融ポリマーを濾過する。濾過された溶融ポリマーを口金に導いてシート状に押出し、これを静電印加法などによって鏡面ドラム上で急冷して非晶シートを得る。その際、溶融ポリマーの温度は２７０〜３００℃とすることが好ましい。また、ポリマーの溶融状態での押出しまでの滞留時間は３０分以下とすることが好ましい。ポリマーの温度と滞留時間をこの範囲とすることで、ポリマーの分子量の低下を抑え、最終的に得られるフィルムのポリマーの数平均分子量を１２０００〜１７０００の範囲とすることができる。得られた非晶シートを、少なくとも１軸方向、好ましくは２軸方向に延伸する。延伸は逐次２軸延伸でおこなっても同時２軸延伸でおこなってもよい。逐次２軸延伸する場合、未延伸フィルムを７０〜１２０℃程度に加熱したロールによって加熱し、回転速度の異なるロール間で長手方向に延伸する。延伸倍率は２〜５倍程度が好ましい。このようにしてフィルム長手方向に延伸したフィルムは一旦冷却し、ついでフィルムの両端をクリップで把持しながらテンターに導き、９０〜１５０℃に加熱した雰囲気中でフィルムを横方向に延伸する。延伸倍率は２〜５倍程度が好ましい。横延伸が終了したフィルムを、寸法安定性を付与するために、さらに１５０〜２３０℃の範囲で熱固定し室温まで冷却することによって、本発明の太陽電池裏面保護シート用白色ポリエステルフィルムを得ることができる。 Polyethylene terephthalate having an intrinsic viscosity of 0.50 to 0.58 and titanium oxide particles are melt-extruded by an extruder, and the molten polymer is filtered by a filter as necessary. The filtered molten polymer is guided to a die and extruded into a sheet shape, which is rapidly cooled on a mirror drum by an electrostatic application method or the like to obtain an amorphous sheet. In that case, it is preferable that the temperature of a molten polymer shall be 270-300 degreeC. Moreover, it is preferable that the residence time until the extrusion in the molten state of the polymer is 30 minutes or less. By setting the temperature and residence time of the polymer within this range, the decrease in the molecular weight of the polymer can be suppressed, and the number average molecular weight of the polymer of the finally obtained film can be set within the range of 12000 to 17000. The obtained amorphous sheet is stretched in at least a uniaxial direction, preferably in a biaxial direction. Stretching may be performed by sequential biaxial stretching or simultaneous biaxial stretching. When sequentially biaxially stretching, the unstretched film is heated by a roll heated to about 70 to 120 ° C., and stretched in the longitudinal direction between rolls having different rotational speeds. The draw ratio is preferably about 2 to 5 times. The film stretched in the longitudinal direction of the film in this way is once cooled, then guided to a tenter while holding both ends of the film with clips, and stretched in the transverse direction in an atmosphere heated to 90 to 150 ° C. The draw ratio is preferably about 2 to 5 times. In order to provide dimensional stability, the film after the transverse stretching is further heat-set in the range of 150 to 230 ° C. and cooled to room temperature, thereby obtaining the white polyester film for the solar cell back surface protective sheet of the present invention. Can do.
以下、本発明を実施例によりさらに詳細に説明する。
（１）フィルム厚み
フィルムサンプルをエレクトリックマイクロメーター（アンリツ製 Ｋ−４０２Ｂ）にて、１０点厚みを測定し、平均値をフィルム厚みとした。
Hereinafter, the present invention will be described in more detail with reference to examples.
(1) Film thickness 10-point thickness was measured for the film sample with an electric micrometer (K-402B manufactured by Anritsu), and the average value was defined as the film thickness.
（２）光学濃度
マクベス社製光学濃度計ＴＲ９２７（透過）を用いて測定した。光源として、ＯＳＲＡＭ社製ランプ１２Ｖ/５０Ｗを用いた。
(2) Optical density It measured using the optical density meter TR927 (transmission) by a Macbeth company. An OSRAM lamp 12V / 50W was used as the light source.
（３）ポリエチレンテレフタレートの数平均分子量
白色ポリエステルフィルム１ｍｇにＨＦＩＰ：クロロホルム（１：１）０．５ｍｌを加えて溶解（一晩）させ、測定直前にクロロホルムを９．５ｍｌを加えて、メンブレンフィルター０．１μｍでろ過しＧＰＣ分析を行った。測定機器、条件は以下のとおりである。
ＧＰＣ：ＨＬＣ−８０２０ 東ソー製
検出器：ＵＶ−８０１０ 東ソー製
カラム：ＴＳＫ−ｇｅｌＧＭＨＨＲ・Ｍ×２ 東ソー製
移動相：ＨＰＬＣ用クロロホルム
流速：１．０ｍｌ／ｍｉｎ
カラム温度：４０℃
検出器：ＵＶ（２５４ｎｍ）
注入量：２００μｌ
較正曲線用試料：ポリスチレン（Ｐｏｌｙｍｅｒ Ｌａｂｏｒａｔｏｒｉｅｓ製ＥａｓｉＣａｌ“ＰＳ−１”）
(3) Number average molecular weight of polyethylene terephthalate 0.5 ml of HFIP: chloroform (1: 1) was added to 1 mg of the white polyester film and dissolved (overnight), and 9.5 ml of chloroform was added immediately before the measurement, and membrane filter 0 The solution was filtered through 1 μm and subjected to GPC analysis. Measuring equipment and conditions are as follows.
GPC: HLC-8020 manufactured by Tosoh Detector: UV-8010 manufactured by Tosoh Column: TSK-gel GMHHR · M × 2 manufactured by Tosoh Mobile phase: chloroform for HPLC Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Detector: UV (254 nm)
Injection volume: 200 μl
Sample for calibration curve: Polystyrene (EasiCal “PS-1” manufactured by Polymer Laboratories)
（４）デラミネーション強度（初期値）
幅１５ｍｍの短冊状にスリットした試料をノンキャリアー粘着テープ（厚み２５μｍ、日栄化工株式会社製、ＭＨＭ−２５）を介してガラス板に貼着し、１８０℃、３０分熱風乾燥して粘着剤を硬化させたものを用いた。これを引張試験機にセットし、引張速度５００ｍｍ／ｍｉｎの速度で１８０°剥離し、フィルム内に強制的にデラミネーションを発生させた。デラミネーションが起こっている状態での剥離力を読み取り、デラミネーション強度とした（単位は、Ｎ／１５ｍｍ）。なお、剥離後のフィルム試料表面を顕微鏡観察し、フィルム内部でのデラミネーションが発生していない場合（粘着剤との界面剥離や接着剤内部のデラミネーションが発生している場合）は、デラミネーション強度はそのとき観測された剥離強度以上とした。
(4) Delamination strength (initial value)
A sample slit in a strip shape with a width of 15 mm was attached to a glass plate via a non-carrier adhesive tape (thickness 25 μm, manufactured by Nihon Kaiko Co., Ltd., MHM-25), and dried with hot air at 180 ° C. for 30 minutes to give an adhesive. A cured product was used. This was set in a tensile tester and peeled 180 ° at a tensile speed of 500 mm / min to forcibly generate delamination in the film. The peel force in the state where delamination occurred was read and taken as delamination strength (unit: N / 15 mm). In addition, when the film sample surface after peeling is observed with a microscope and delamination does not occur inside the film (when interfacial peeling from the adhesive or delamination inside the adhesive occurs), delamination The strength was higher than the observed peel strength.
（５）デラミネーション強度（耐候試験後）
８５℃・８５％ＲＨの雰囲気にフィルムを１０００時間保持した後、上記（４）と同様の方法でサンプルを作成して、１８０°剥離してデラミネーション強度を測定した（単位はＮ／１５ｍｍ）。
(5) Delamination strength (after weathering test)
After holding the film in an atmosphere of 85 ° C. and 85% RH for 1000 hours, a sample was prepared by the same method as in (4) above, peeled 180 °, and the delamination strength was measured (unit: N / 15 mm) .
（６）ポリエチレンテレフタレートの固有粘度
オルトクロロフェノール溶媒に加熱溶解させ２５℃で測定した。
(6) Intrinsic viscosity of polyethylene terephthalate It was heated and dissolved in an orthochlorophenol solvent and measured at 25 ° C.
（７）延伸性
長手方向３．０倍、横方向３．７倍に延伸してフィルムを製膜し、その際に、安定して製膜できるか観察した。下記基準で評価した。
○：１時間以上安定して製膜できる。
△：１０分間以上安定して製膜できるが、１時間経過する前に切断が発生する。
×：１０分間経過する前に切断が発生し、安定した製膜ができない。
(7) Stretchability A film was formed by stretching 3.0 times in the longitudinal direction and 3.7 times in the transverse direction, and at that time, it was observed whether the film could be stably formed. Evaluation was made according to the following criteria.
○: A film can be stably formed for 1 hour or more.
Δ: Film can be stably formed for 10 minutes or more, but cutting occurs before 1 hour elapses.
X: Cutting occurred before 10 minutes passed, and stable film formation was not possible.
（８）二酸化チタン粒子の平均粒径
ＨＯＲＩＢＡ製ＬＡ−７５０パーティクルサイズアナライザー（Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ａｎａｌｙｚｅｒ）を用いて測定した。５０マスパーセントに相当する粒子径を読み取り、この値を平均粒径とした。
(8) Average particle diameter of titanium dioxide particles The average particle diameter of titanium dioxide particles was measured using an LA-750 particle size analyzer (Particle Size Analyzer) manufactured by HORIBA. The particle diameter corresponding to 50 mass percent was read, and this value was taken as the average particle diameter.
［実施例１］
エステル交換反応容器にジメチルテレフタレートを１００重量部、エチレングリコールを６１重量部、酢酸マグネシウム四水塩を０．０６重量部仕込み、１５０℃に加熱して溶融し撹拌した。反応容器内温度をゆっくりと２３５℃まで昇温しながら反応を進め、生成するメタノールを反応容器外へ留出させた。メタノールの留出が終了したらトリメチルリン酸を０．０２重量部添加した。トリメチルリン酸を添加した後、三酸化アンチモンを０．０３重量部添加し、反応物を重合装置に移行した。ついで重合装置内の温度を２３５℃から２９０℃まで９０分かけて昇温し、同時に装置内の圧力を大気圧から１００Ｐａまで９０分かけて減圧した。重合装置内容物の撹拌トルクが所定の値に達したら装置内を窒素ガスで大気圧に戻して重合を終了した。重合装置下部のバルブを開いて重合装置内部を窒素ガスで加圧し、重合の完了したポリエチレンテレフタレートをストランド状にして水中に吐出した。ストランドはカッターによってチップ化した。このようにして固有粘度が０．５０ｄｌ／ｇであるポリエチレンテレフタレートのポリマーを得た。これをＰＥＴ−Ａと称する。
[Example 1]
A transesterification vessel was charged with 100 parts by weight of dimethyl terephthalate, 61 parts by weight of ethylene glycol, and 0.06 part by weight of magnesium acetate tetrahydrate, heated to 150 ° C., melted and stirred. The reaction was advanced while the temperature inside the reaction vessel was slowly raised to 235 ° C., and the methanol produced was distilled out of the reaction vessel. When the distillation of methanol was completed, 0.02 part by weight of trimethyl phosphoric acid was added. After adding trimethyl phosphoric acid, 0.03 part by weight of antimony trioxide was added, and the reaction product was transferred to a polymerization apparatus. Subsequently, the temperature in the polymerization apparatus was raised from 235 ° C. to 290 ° C. over 90 minutes, and at the same time, the pressure in the apparatus was reduced from atmospheric pressure to 100 Pa over 90 minutes. When the stirring torque of the contents of the polymerization apparatus reached a predetermined value, the interior of the apparatus was returned to atmospheric pressure with nitrogen gas to complete the polymerization. The valve at the bottom of the polymerization apparatus was opened and the inside of the polymerization apparatus was pressurized with nitrogen gas, and the polymerized polyethylene terephthalate was discharged into water in the form of a strand. The strand was chipped with a cutter. In this way, a polyethylene terephthalate polymer having an intrinsic viscosity of 0.50 dl / g was obtained. This is referred to as PET-A.
得られたＰＥＴ−Ａの４０重量部と、平均粒径０．２μｍのアナターゼ型二酸化チタン粒子の６０重量部とをブレンドし、２軸混練機に供給して２８０℃で溶融した。溶融混練したポリエチレンテレフタレート組成物をストランド状に水中に吐出し、カッターによってチップ化した。これをＰＥＴ−Ｂと称する。 40 parts by weight of the obtained PET-A and 60 parts by weight of anatase-type titanium dioxide particles having an average particle diameter of 0.2 μm were blended, supplied to a biaxial kneader, and melted at 280 ° C. The melt-kneaded polyethylene terephthalate composition was discharged into water in the form of a strand and formed into chips by a cutter. This is referred to as PET-B.
ＰＥＴ−ＡとＰＥＴ−Ｂとを、混合物での二酸化チタン粒子含有量が７重量％となるように混合し、回転式真空乾燥機にて１８０℃で３時間乾燥した。乾燥の終了したチップを押出し機に供給して２８０℃で溶融押出しし、ダイスよりシート状に成形した。その際、ポリマーの溶融状態での押出しまでの滞留時間は２０分となるように押出し量を調整した。さらに、このシート状のポリマーを表面温度２５℃の冷却ドラムで冷却固化して未延伸フィルムとし、これを１００℃にて長手方向（縦方向）に３．０倍延伸し、２５℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１３０℃に加熱された雰囲気中で長手方向に垂直な方向（横方向）に３．７倍延伸した。その後テンター内で２２０℃に加熱された雰囲気中で熱固定を行い、横方向に２％の幅入れを行い、室温まで冷やして白色ポリエステルフィルムを得た。得られたフィルムの物性は表１のとおりであった。 PET-A and PET-B were mixed so that the titanium dioxide particle content in the mixture was 7% by weight, and dried at 180 ° C. for 3 hours in a rotary vacuum dryer. The dried chips were supplied to an extruder, melt-extruded at 280 ° C., and formed into a sheet from a die. At that time, the amount of extrusion was adjusted so that the residence time until extrusion in the molten state of the polymer was 20 minutes. Further, this sheet-like polymer was cooled and solidified with a cooling drum having a surface temperature of 25 ° C. to obtain an unstretched film, which was stretched 3.0 times in the longitudinal direction (longitudinal direction) at 100 ° C., and a roll group at 25 ° C. It was cooled with. Subsequently, while holding both ends of the longitudinally stretched film with clips, the film was stretched 3.7 times in the direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 130 ° C. guided to a tenter. Thereafter, heat setting was performed in an atmosphere heated to 220 ° C. in a tenter, a width of 2% was applied in the transverse direction, and the mixture was cooled to room temperature to obtain a white polyester film. Table 1 shows the physical properties of the obtained film.
［実施例２〜７、比較例１〜６］
ＰＥＴ−Ａの固有粘度、二酸化チタン粒子の含有量、フィルム厚みを表１に示すとおりに変更した以外は、実施例１と同様にして白色ポリエステルフィルムを得た。得られたフィルムの物性は表１のとおりであった。
[Examples 2-7, Comparative Examples 1-6]
A white polyester film was obtained in the same manner as in Example 1 except that the intrinsic viscosity of PET-A, the content of titanium dioxide particles, and the film thickness were changed as shown in Table 1. Table 1 shows the physical properties of the obtained film.
［比較例７］
乾燥の終了したチップを押出し機に供給し３１０℃で溶融押出しした以外は、実施例３と同様にして白色ポリエステルフィルムを得た。得られたフィルムの物性は表１のとおりであった。
[Comparative Example 7]
A white polyester film was obtained in the same manner as in Example 3 except that the dried chips were supplied to an extruder and melt-extruded at 310 ° C. Table 1 shows the physical properties of the obtained film.
［比較例８］
ポリマーの溶融状態での押出しまでの滞留時間が５０分となるように押出し量を調整した以外は、実施例３と同様にして白色ポリエステルフィルムを得た。得られたフィルムの物性は表１のとおりであった。
[Comparative Example 8]
A white polyester film was obtained in the same manner as in Example 3 except that the amount of extrusion was adjusted so that the residence time until extrusion in the molten state of the polymer was 50 minutes. Table 1 shows the physical properties of the obtained film.
本発明の太陽電池裏面保護シート用白色ポリエステルフィルムは、太陽電池ユニットを構成する部材である太陽電池裏面保護シートとして最適に用いることができる。 The white polyester film for a solar cell back surface protective sheet of the present invention can be optimally used as a solar cell back surface protective sheet which is a member constituting a solar cell unit.
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