JP2009137012A - Laminate, sheet for protecting surface of solar battery, and building material sheet - Google Patents

Laminate, sheet for protecting surface of solar battery, and building material sheet Download PDF

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JP2009137012A
JP2009137012A JP2006086174A JP2006086174A JP2009137012A JP 2009137012 A JP2009137012 A JP 2009137012A JP 2006086174 A JP2006086174 A JP 2006086174A JP 2006086174 A JP2006086174 A JP 2006086174A JP 2009137012 A JP2009137012 A JP 2009137012A
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laminate
sheet
fluorine
film
adhesive layer
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Shigesato Mukai
恵吏 向井
Tatsuya Higuchi
達也 樋口
Masami Kato
雅巳 加藤
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2006086174A priority Critical patent/JP2009137012A/en
Priority to PCT/JP2007/056228 priority patent/WO2007116688A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide, for example, a weight-reduced laminate excellent in weatherability, durability, impact resistance, etc. <P>SOLUTION: The laminate is formed by laminating a fluorocarbon resin film 1, an adhesive layer 2 containing an ultraviolet absorber, and a resin sheet 3 containing no fluorine in turn and has a total light transmittance of at least 85%. A fluorocarbon resin polymer constituting the fluorocarbon resin film 1 is selected from a group consisting of an ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene and tetrafluoroethylene/hexafluoropropylene. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、積層体、太陽電池表面保護シート及び建材シートに関する。 The present invention relates to a laminate, a solar cell surface protective sheet, and a building material sheet.

フッ素樹脂は、耐侯性に優れているので、太陽電池や建材等の部材として利用されている。
例えば、エチレン／酢酸ビニル共重合体〔ＥＶＡ〕等の充填材に高分子樹脂フィルムを積層させて太陽電池素子を保護した太陽電池モジュールにおいて、高分子樹脂フィルムとして特定のフッ素樹脂フィルムを使用することが提案されている（例えば、特許文献１参照）。しかしながら、この太陽電池モジュールには、高分子樹脂フィルムが薄いと、外部からの衝撃に劣り、太陽電池素子を充分保護することができない問題があった。 Since the fluororesin is excellent in weather resistance, it is used as a member for solar cells and building materials.
For example, in a solar cell module in which a polymer resin film is laminated on a filler such as ethylene / vinyl acetate copolymer [EVA] to protect a solar cell element, a specific fluororesin film is used as the polymer resin film. Has been proposed (see, for example, Patent Document 1). However, this solar cell module has a problem that when the polymer resin film is thin, it is inferior in impact from the outside and cannot sufficiently protect the solar cell element.

フッ素樹脂を用いた太陽電池用セルのカバー材として、透明高耐光フィルムとしてのフッ素樹脂フィルムと、ポリエチレンテレフタレート〔ＰＥＴ〕フィルム等の透明高防湿フィルムとを、紫外線吸収剤等を配合したＥＶＡ系接着剤で積層させたものが提案されている（例えば、特許文献２参照。）。しかしながら、このカバー材は、使用する透明高防湿フィルムの特性上、耐衝撃性、燃焼性、耐侯性等に劣ることがある。
特開昭６３−９９５８１号公報 特開２０００−１７４２９８号公報 EVA-based adhesion in which UV resin is blended with fluororesin film as transparent high light-resistant film and transparent high moisture-proof film such as polyethylene terephthalate [PET] film as cover material for solar cell using fluororesin The thing laminated | stacked with the agent is proposed (for example, refer patent document 2). However, this cover material may be inferior in impact resistance, flammability, weather resistance, etc. on the characteristic of the transparent highly moisture-proof film to be used.
JP 63-99581 A JP 2000-174298 A

本発明の目的は、上記現状に鑑み、耐候性、耐久性、耐衝撃性等に優れ、軽量化された積層体等の提供にある。 An object of the present invention is to provide a laminate and the like that are excellent in weather resistance, durability, impact resistance, and the like in light of the current situation.

本発明は、フッ素樹脂フィルム（Ａ）、紫外線吸収剤を含む接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）がこの順で積層されてなり全光線透過率が８５％以上であることを特徴とする積層体である。
本発明は、上記本発明の積層体からなることを特徴とする太陽電池表面保護シートである。
本発明は、上記本発明の積層体からなることを特徴とする建材シートである。
以下に本発明を詳細に説明する。 In the present invention, the fluororesin film (A), the adhesive layer (B) containing an ultraviolet absorber, and the fluorine-free resin sheet (C) are laminated in this order, and the total light transmittance is 85% or more. It is the laminated body characterized by these.
This invention is a solar cell surface protection sheet characterized by consisting of the laminated body of the said invention.
The present invention is a building material sheet comprising the laminate of the present invention.
The present invention is described in detail below.

本発明の積層体は、フッ素樹脂フィルム（Ａ）、紫外線吸収剤を含む接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）がこの順で積層されてなるものである。
上記積層体は、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）のみからなりこの順で積層されてなる３層構造の積層体であってもよいし、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）を少なくとも含むものであれば、更に層を含むものであってもよい。
該更に層を含む上記積層体としては特に限定されず、例えば、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）、フッ素非含有樹脂シート（Ｃ）、接着剤層（Ｂ）及びフッ素樹脂フィルム（Ａ）がこの順に積層されてなる５層構造の積層体等が挙げられる。
上記積層体は、フッ素樹脂フィルム（Ａ）と接着剤層（Ｂ）との間、接着剤層（Ｂ）とフッ素非含有樹脂シート（Ｃ）との間が、それぞれ充分に接着しているものである。 The laminate of the present invention comprises a fluororesin film (A), an adhesive layer (B) containing an ultraviolet absorber, and a fluorine-free resin sheet (C) laminated in this order.
The laminate may be a laminate having a three-layer structure composed of only the fluororesin film (A), the adhesive layer (B) and the fluorine-free resin sheet (C) and laminated in this order. As long as it includes at least the fluororesin film (A), the adhesive layer (B), and the fluorine-free resin sheet (C), it may further include a layer.
The laminate including the layers is not particularly limited, and examples thereof include a fluororesin film (A), an adhesive layer (B), a fluorine-free resin sheet (C), an adhesive layer (B), and a fluororesin film. A laminate having a five-layer structure in which (A) is laminated in this order is exemplified.
The laminate is sufficiently bonded between the fluororesin film (A) and the adhesive layer (B) and between the adhesive layer (B) and the fluorine-free resin sheet (C). It is.

フッ素樹脂フィルム（Ａ）を構成するフッ素樹脂ポリマーは、特に限定されないが、エチレン／テトラフルオロエチレン共重合体〔ＥＴＦＥ〕、ポリクロロトリフルオロエチレン〔ＰＣＴＦＥ〕及びテトラフルオロエチレン／ヘキサフルオロプロピレン共重合体〔ＦＥＰ〕よりなる群から選ばれる少なくとも１つであることが好ましい。
上記フルオロポリマーは、上記例示した各単量体のみならず、これら該各単量体と共重合可能な共単量体をも含む３元以上の共重合体であってもよい。上記ＦＥＰは、例えば、エチレン／テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体等をも含み得る概念である。
上記フッ素樹脂ポリマーは、懸濁重合、溶液重合、乳化重合、塊状重合等、従来公知の方法で調製することができる。各重合の条件は、調製するフッ素樹脂ポリマーの組成や量に応じて適宜選択することができる。 The fluororesin polymer constituting the fluororesin film (A) is not particularly limited, but ethylene / tetrafluoroethylene copolymer [ETFE], polychlorotrifluoroethylene [PCTFE], and tetrafluoroethylene / hexafluoropropylene copolymer. It is preferably at least one selected from the group consisting of [FEP].
The fluoropolymer may be a ternary or higher copolymer including not only the above-exemplified monomers but also comonomer copolymerizable with these monomers. The FEP is a concept that may include, for example, an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer.
The fluororesin polymer can be prepared by a conventionally known method such as suspension polymerization, solution polymerization, emulsion polymerization, bulk polymerization and the like. The conditions for each polymerization can be appropriately selected according to the composition and amount of the fluororesin polymer to be prepared.

上記フッ素樹脂フィルム（Ａ）は、厚みが５〜５００μｍであることが好ましい。上記厚みが５μｍ未満である場合、取り扱い性が悪化したり、歩留まりが低下したりすることがあり、上記厚みが５００μｍを越えると、コストが高くなることがある。
上記厚みは、より好ましい下限が１２μｍであり、より好ましい上限が５０μｍである。
本明細書において、上記フッ素樹脂フィルム（Ａ）等の各層の厚みは、マイクロゲージを用いて測定したものである。 The fluororesin film (A) preferably has a thickness of 5 to 500 μm. When the thickness is less than 5 μm, the handleability may be deteriorated and the yield may be lowered. When the thickness exceeds 500 μm, the cost may be increased.
A more preferable lower limit of the thickness is 12 μm, and a more preferable upper limit is 50 μm.
In this specification, the thickness of each layer such as the fluororesin film (A) is measured using a micro gauge.

上記フッ素樹脂フィルム（Ａ）は、上記フッ素樹脂ポリマーを用いて、従来公知の方法で作成することができ、市販品として入手することもできる。
上記フッ素樹脂フィルム（Ａ）は、層間接着性の点で、少なくとも接着剤層（Ｂ）側の面をプラズマ処理したものが好ましい。上記プラズマ処理については、後述する。 The said fluororesin film (A) can be created by a conventionally well-known method using the said fluororesin polymer, and can also be obtained as a commercial item.
The fluororesin film (A) is preferably one in which at least the surface on the adhesive layer (B) side is plasma-treated in terms of interlayer adhesion. The plasma treatment will be described later.

上記接着剤層（Ｂ）を構成する接着剤は、特に限定されないが、エチレン／酢酸ビニル共重合体〔ＥＶＡ〕、ポリビニルアセタール樹脂及びシリコーン樹脂よりなる群から選ばれる少なくとも１つであることが好ましい。
上記ポリビニルアセタール樹脂としては、例えば、ポリビニルブチラール樹脂〔ＰＶＢ〕、ポリビニルアセトアセタール樹脂（ＰＶＢのブチルアルデヒドに代え、アセトアルデヒドを付加縮合させたもの）等が挙げられ、ＰＶＢが好ましい。
上記接着剤層（Ｂ）を構成する接着剤としては、汎用性の点で、ＥＶＡ、ＰＶＢ等がより好ましい。 The adhesive constituting the adhesive layer (B) is not particularly limited, but is preferably at least one selected from the group consisting of an ethylene / vinyl acetate copolymer [EVA], a polyvinyl acetal resin, and a silicone resin. .
Examples of the polyvinyl acetal resin include polyvinyl butyral resin [PVB], polyvinyl acetoacetal resin (a product obtained by adding and condensing acetaldehyde instead of PVB butyraldehyde), and PVB is preferable.
As an adhesive which comprises the said adhesive bond layer (B), EVA, PVB, etc. are more preferable at the point of versatility.

本発明において、接着剤層（Ｂ）は、紫外線吸収剤を含むものである。
該紫外線吸収剤としては、特に限定されず、例えば、ベンゾフェノン系紫外線吸収剤、ヒンダートアミン系紫外線吸収剤等が挙げられる。
上記接着剤層（Ｂ）において、紫外線吸収剤は、接着剤１００質量部に対し０．０５〜２０質量部であることが好ましく、０．１〜１０質量部であることがより好ましい。
上記紫外線吸収剤は、耐候性向上の点で、接着剤層（Ｂ）のみならず、更にフッ素樹脂フィルム（Ａ）及び／又はフッ素非含有樹脂シート（Ｃ）にも含有させてもよいが、効率良く耐候性を向上し得る点で、接着剤層（Ｂ）のみに含有させることとしても、本発明の積層体全体として良好な耐候性を奏することができる。 In the present invention, the adhesive layer (B) contains an ultraviolet absorber.
The ultraviolet absorber is not particularly limited, and examples thereof include benzophenone ultraviolet absorbers and hindered amine ultraviolet absorbers.
In the said adhesive bond layer (B), it is preferable that it is 0.05-20 mass parts with respect to 100 mass parts of adhesives, and, as for an ultraviolet absorber, it is more preferable that it is 0.1-10 mass parts.
The ultraviolet absorber may be contained not only in the adhesive layer (B) but also in the fluororesin film (A) and / or the fluorine-free resin sheet (C) in terms of improving weather resistance. Even if it is contained only in the adhesive layer (B), the weatherability as a whole of the laminate of the present invention can be exhibited in that the weather resistance can be improved efficiently.

上記紫外線吸収剤を含む接着剤層（Ｂ）としては、接着剤と紫外線吸収剤とからなる塗工液を用いて形成することもできるし、用いる接着剤によっては、予め紫外線吸収剤を添加してなる市販品を用いて形成することもできる。
上記接着剤層（Ｂ）としては、例えば、ＥＶＡの場合、紫外線吸収剤入りの市販品がある。
上記接着剤層（Ｂ）は、厚みが１〜６００μｍであることが好ましくは、５〜４００μｍであることがより好ましい。 The adhesive layer (B) containing the ultraviolet absorber can be formed using a coating liquid composed of an adhesive and an ultraviolet absorber. Depending on the adhesive to be used, an ultraviolet absorber may be added in advance. It can also be formed using a commercially available product.
As said adhesive bond layer (B), in the case of EVA, there exists a commercial item containing a ultraviolet absorber.
The adhesive layer (B) preferably has a thickness of 1 to 600 μm, more preferably 5 to 400 μm.

上記フッ素非含有樹脂シート（Ｃ）を構成するフッ素非含有樹脂としては、例えば、アクリル樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート〔ＰＥＴ〕、ポリエチレンナフタレート〔ＰＥＮ〕、ポリ塩化ビニル、ポリアミド樹脂、ポリプロピレン、ポリエチレン、環状ポリオレフィン、スチレン系共重合体等が挙げられるが、なかでも、耐侯性、耐衝撃性、不燃性の点で、ポリカーボネート樹脂が好ましい。 Examples of the fluorine-free resin constituting the fluorine-free resin sheet (C) include acrylic resin, polycarbonate resin, polyethylene terephthalate [PET], polyethylene naphthalate [PEN], polyvinyl chloride, polyamide resin, polypropylene, and polyethylene. , Cyclic polyolefins, styrene copolymers, etc., among which polycarbonate resins are preferred in terms of weather resistance, impact resistance, and incombustibility.

上記フッ素非含有樹脂シート（Ｃ）は、厚みが３０μｍ〜７ｍｍであることが好ましい。上記厚みが３０μｍ未満であると、耐衝撃性に劣ることがあり、上記厚みが７ｍｍを越えると、光線透過率が低下することがある。
上記厚みは、より好ましい下限が５０μｍであり、より好ましい上限が５ｍｍである。
上記フッ素非含有樹脂シート（Ｃ）は、従来公知の方法で作成することができ、また市販品であってもよい。
上記フッ素非含有樹脂シート（Ｃ）は、上記紫外線吸収剤を含む接着剤層（Ｂ）がＥＶＡであるとき、表面処理を施してもよいが、施さなくても充分な層間接着性があるので、表面処理を施す必要はない。
上記フッ素非含有樹脂シート（Ｃ）は、上記紫外線吸収剤を含む接着剤層（Ｂ）が例えばＰＶＢであるとき、層間接着性の点で、圧着ラミネートを行う前に、少なくとも接着剤層（Ｂ）側の面を表面処理することが好ましく、該表面処理としては、プラズマ処理が好ましい。 The fluorine-free resin sheet (C) preferably has a thickness of 30 μm to 7 mm. When the thickness is less than 30 μm, the impact resistance may be inferior, and when the thickness exceeds 7 mm, the light transmittance may be lowered.
A more preferable lower limit of the thickness is 50 μm, and a more preferable upper limit is 5 mm.
The fluorine-free resin sheet (C) can be prepared by a conventionally known method or may be a commercially available product.
The fluorine-free resin sheet (C) may be subjected to surface treatment when the adhesive layer (B) containing the ultraviolet absorber is EVA, but has sufficient interlayer adhesion even if it is not applied. It is not necessary to apply surface treatment.
When the adhesive layer (B) containing the ultraviolet absorber is, for example, PVB, the fluorine-free resin sheet (C) is at least an adhesive layer (B ) Side surface is preferably surface-treated, and the surface treatment is preferably plasma treatment.

本発明の積層体は、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）に加え、更に、防湿層（Ｄ）をも含むものであってもよい。該防湿層（Ｄ）としては特に限定されず、例えば、フッ素樹脂フィルム（Ａ）の接着剤層（Ｂ）側に積層させてもよいし、フッ素非含有樹脂シート（Ｃ）の接着剤層（Ｂ）側に積層させてもよい。 The laminate of the present invention may further include a moisture-proof layer (D) in addition to the fluororesin film (A), the adhesive layer (B) and the fluorine-free resin sheet (C). The moisture-proof layer (D) is not particularly limited. For example, the moisture-proof layer (D) may be laminated on the adhesive layer (B) side of the fluororesin film (A), or the adhesive layer of the fluorine-free resin sheet (C) ( It may be laminated on the B) side.

上記防湿層（Ｄ）としては、例えば、シリカ、アルミナ等の無機酸化物からなるものが好ましい。
上記防湿層（Ｄ）は、使用する無機酸化物の種類等により異なるが、厚みが０．００１〜０．５μｍであることが好ましく、０．０１〜０．１μｍであることがより好ましい。 As said moisture-proof layer (D), what consists of inorganic oxides, such as a silica and an alumina, for example is preferable.
Although the moisture-proof layer (D) varies depending on the type of inorganic oxide used, the thickness is preferably 0.001 to 0.5 μm, and more preferably 0.01 to 0.1 μm.

上記防湿層（Ｄ）を設ける場合、該防湿層（Ｄ）は、例えば、フッ素樹脂フィルム（Ａ）及び／又はフッ素非含有樹脂シート（Ｃ）等の積層対象に積層してから接着剤層（Ｂ）を介在させて本発明の積層体を形成することが好ましい。
上記防湿層（Ｄ）の上記積層対象への積層は、防湿性と層間接着力の点で、上記フッ素樹脂フィルム（Ａ）及び／又はフッ素非含有樹脂シート（Ｃ）等の積層対象にプラズマ処理等の表面処理を施す前に積層することが好ましい。
上記防湿層（Ｄ）の上記積層対象への積層は、例えば、物理蒸着法、化学蒸着法等により、積層する防湿層（Ｄ）、積層対象の種類等に応じて適宜条件を選択して行うことができる。 When providing the moisture-proof layer (D), the moisture-proof layer (D) is, for example, laminated on an object to be laminated such as a fluororesin film (A) and / or a fluorine-free resin sheet (C). It is preferable to form the laminate of the present invention with B) interposed.
The moisture-proof layer (D) is laminated on the lamination object by plasma treatment on the lamination object such as the fluorine resin film (A) and / or fluorine-free resin sheet (C) in terms of moisture resistance and interlayer adhesion. It is preferable to laminate before surface treatment such as the above.
Lamination of the moisture-proof layer (D) to the stacking target is performed by appropriately selecting conditions according to the moisture-proof layer (D) to be stacked, the type of stacking target, and the like by, for example, physical vapor deposition or chemical vapor deposition. be able to.

本発明の積層体は、全光線透過率が８０％以上であってもよいが、好ましくは８５％以上であるものである。
上記全光線透過率は、上記範囲内であれば９０％であってもよい。
本明細書において、上記全光線透過率は、作成後、未使用の積層体について測定するものであり、ヘイズガードＩＩ（東洋精機製作所製）を用いて測定したものである。 The laminate of the present invention may have a total light transmittance of 80% or more, but preferably 85% or more.
The total light transmittance may be 90% within the above range.
In the present specification, the total light transmittance is measured with respect to an unused laminate after preparation, and is measured using Hazeguard II (manufactured by Toyo Seiki Seisakusho).

本発明の積層体は、例えば、
（１）フッ素樹脂フィルム（Ａ）とフッ素非含有樹脂シート（Ｃ）との間に、予め作成した接着剤層（Ｂ）フィルムを挟むようにして重ね、圧着ラミネートを行う、
（２）接着剤と紫外線吸収剤とからなる塗工液を、フッ素樹脂フィルム（Ａ）及びフッ素非含有樹脂シート（Ｃ）に塗布し、乾燥させた後に、フッ素樹脂フィルム（Ａ）及びフッ素非含有樹脂シート（Ｃ）の上記各塗布面が接するように圧着ラミネートを行う、
等の方法を用い、各層を積層させることにより作成することができる。 The laminate of the present invention is, for example,
(1) Between the fluororesin film (A) and the non-fluorine-containing resin sheet (C), the adhesive layer (B) film prepared in advance is overlapped and subjected to pressure laminating.
(2) A coating liquid composed of an adhesive and an ultraviolet absorber is applied to the fluororesin film (A) and the fluorine-free resin sheet (C) and dried, and then the fluororesin film (A) and the fluororesin Pressure bonding laminating so that each application surface of the containing resin sheet (C) is in contact,
It can produce by laminating | stacking each layer using methods, such as.

上記フッ素樹脂フィルム（Ａ）及びフッ素非含有樹脂シート（Ｃ）は、上述のように、それぞれ必要に応じ、圧着ラミネートを行う前に表面にプラズマ処理を行うことが好ましい。
フッ素樹脂フィルム（Ａ）表面ないしフッ素非含有樹脂シート（Ｃ）表面に施す上記プラズマ処理は、例えば、特開昭５９−２１７７３１号公報、特開平４−３４９６７２号公報等に記載の方法により行うことができる。
プラズマ発生の原料ガスとしては、例えば、Ａｒガス、Ｈｅガス、Ｈ２ガス、Ｏ２ガス、Ｎ２ガス、ＮＨ３ガス若しくは炭化水素ガス、又は、これらの混合ガス等が挙げられる。
上記プラズマ処理は、処理対象、使用するプラズマ発生源の種類等に応じて、適宜条件を選択して行うことができ、特に限定されないが、５〜７００Ｐａ、好ましくは１０〜３００Ｐａの圧力下で、１０〜４０℃、好ましくは１５〜２５℃にて行うことが好ましい。
上記プラズマ処理において、処理の強さ、すなわち処理強度は特に限定されないが、処理強度が０．１〜３００Ｗ・秒／ｃｍ２であることが好ましい。 As described above, the fluororesin film (A) and the non-fluorine-containing resin sheet (C) are preferably subjected to plasma treatment on the surface before the pressure laminating as necessary.
The plasma treatment applied to the surface of the fluororesin film (A) or the non-fluorine-containing resin sheet (C) is performed by the method described in, for example, JP-A-59-217731 and JP-A-4-349672. Can do.
Examples of the source gas for generating plasma include Ar gas, He gas, H 2 gas, O 2 gas, N 2 gas, NH 3 gas, hydrocarbon gas, or a mixed gas thereof.
The plasma treatment can be performed by appropriately selecting conditions according to the object to be treated, the type of plasma generation source to be used, and the like. Although not particularly limited, the pressure is 5 to 700 Pa, preferably 10 to 300 Pa. It is preferable to carry out at 10 to 40 ° C, preferably 15 to 25 ° C.
In the plasma treatment, the strength of the treatment, that is, the treatment strength is not particularly limited, but the treatment strength is preferably 0.1 to 300 W · sec / cm 2 .

フッ素樹脂フィルム（Ａ）表面ないしフッ素非含有樹脂シート（Ｃ）表面に施す上記プラズマ処理は、層間接着性の点で、減圧下に行うものが好ましく、また、Ａｒガス、ＡｒとＨ２との混合ガス又はＮＨ３ガスの雰囲気下に行うものが好ましく、減圧下にＡｒとＨ２との混合ガス又はＮＨ３ガスの存在下に行うものがより好ましい。
ＡｒとＨ２との混合ガスは、ＡｒとＨ２との合計体積に占めるＨ２の体積が１〜７０％であるものが好ましく、１〜２０％であるものがより好ましい。 The plasma treatment applied to the surface of the fluororesin film (A) or the surface of the non-fluorine-containing resin sheet (C) is preferably performed under reduced pressure in terms of interlayer adhesion, and Ar gas, Ar and H 2 What is performed in an atmosphere of mixed gas or NH 3 gas is preferable, and what is performed in the presence of a mixed gas of Ar and H 2 or NH 3 gas under reduced pressure is more preferable.
Gas mixture of Ar and H 2 is preferably one volume of H 2 in the total volume of Ar and H 2 is 1 to 70%, and is more preferable from 1 to 20%.

上記圧着ラミネートは、使用する各層の種類、厚み等に応じて適宜条件を選択して行うことができるが、一般に１３０〜１７０℃の温度下で行うことが好ましい。
上記圧着ラミネートは、更に、好ましくは１５〜１００００Ｐａの圧力下で行うことが好ましい。
上記圧着ラミネートは、一般に１５〜６０分間行う。
本発明の積層体は、全体の厚みが０．０５〜１０ｍｍであることが好ましく、０．１〜５ｍｍであることがより好ましい。 The pressure-bonding laminate can be performed by appropriately selecting conditions according to the type and thickness of each layer to be used, but is generally preferably performed at a temperature of 130 to 170 ° C.
The pressure-bonding lamination is preferably performed under a pressure of 15 to 10000 Pa.
The pressure-bonding lamination is generally performed for 15 to 60 minutes.
The total thickness of the laminate of the present invention is preferably 0.05 to 10 mm, and more preferably 0.1 to 5 mm.

本発明の積層体は、上述の構成からなるものであり、フッ素樹脂フィルム（Ａ）とフッ素非含有樹脂シート（Ｃ）との間の層間接着強度に優れたものである。
上記層間接着強度は、紫外線照射後フッ素樹脂フィルムが破断するときの強度である。例えば、厚さ０．０５ｍｍのＥＴＦＥフィルムでは１３Ｎ／ｃｍ以上で、また、厚さ０．１ｍｍのＰＣＴＦＥフィルムでは２５Ｎ／ｃｍ以上で、更に、厚さ０．０５ｍｍのＦＥＰフィルムでは７Ｎ／ｃｍ以上で、層間剥離せずにフッ素樹脂フィルムが破断する。これらの範囲内であれば、太陽電池保護シート、建材シート等の屋外の使用時にも充分な層間接着強度である。
本発明の積層体は、耐侯性に優れており、促進耐侯試験を後述の条件で１０００時間行った後でも、上記層間接着強度を促進耐侯試験前の値の８５％以上維持することができる。
上記層間接着強度は、（株）オリエンテック製の万能材料試験機ＲＴＣ−１２２５Ａを使用し、ＡＳＴＭ Ｄ８８２に基づいて測定したものである。 The laminate of the present invention has the above-described configuration, and has excellent interlayer adhesive strength between the fluororesin film (A) and the non-fluorine-containing resin sheet (C).
The interlayer adhesive strength is the strength at which the fluororesin film breaks after UV irradiation. For example, it is 13 N / cm or more for an ETFE film having a thickness of 0.05 mm, 25 N / cm or more for a PCTFE film having a thickness of 0.1 mm, and 7 N / cm or more for an FEP film having a thickness of 0.05 mm. The fluororesin film breaks without delamination. Within these ranges, the interlayer adhesion strength is sufficient even when used outdoors such as solar cell protective sheets and building material sheets.
The laminate of the present invention is excellent in weather resistance, and can maintain the above-mentioned interlayer adhesive strength at 85% or more of the value before the accelerated weather resistance test even after the accelerated weather resistance test is performed for 1000 hours under the conditions described later.
The interlayer adhesion strength is measured based on ASTM D882 using a universal material testing machine RTC-1225A manufactured by Orientec Co., Ltd.

本発明の積層体は、更に、耐熱水性にも優れており、例えば、９０℃の熱水に９６時間浸漬した後、ＪＩＳ Ｋ ６８５４に準拠した剥離試験を行っても、フッ素樹脂フィルム（Ａ）とフッ素非含有樹脂シート（Ｃ）とが剥離しない。 The laminate of the present invention is also excellent in hot water resistance. For example, even if it is immersed in hot water at 90 ° C. for 96 hours and then subjected to a peel test in accordance with JIS K 6854, the fluororesin film (A) And the fluorine-free resin sheet (C) do not peel off.

上述の本発明の積層体からなる太陽電池表面保護シートもまた、本発明の一つである。
本発明の太陽電池表面保護シートを構成する上記本発明の積層体としては、一般に、フッ素樹脂フィルム（Ａ）、紫外線吸収剤を含む接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）のみからなりこの順で積層されてなる３層構造の積層体等が挙げられる。
本発明の太陽電池表面保護シートを構成する該３層構造の積層体としては、フッ素非含有樹脂シート（Ｃ）がＰＣシートであるものが特に好ましく、また、フッ素樹脂フィルム（Ａ）を構成するフッ素樹脂がＰＣＴＦＥ、ＥＴＦＥ又はＦＥＰであるものが好ましく、また、接着剤層（Ｂ）を構成する接着剤がＥＶＡ又はＰＶＢであるものが好ましい。 The solar cell surface protective sheet comprising the above-described laminate of the present invention is also one aspect of the present invention.
Generally as a laminated body of the said this invention which comprises the solar cell surface protection sheet of this invention, only the fluorine resin film (A), the adhesive bond layer (B) containing a ultraviolet absorber, and a fluorine-free resin sheet (C) only. And a laminate having a three-layer structure in which the layers are laminated in this order.
As the laminate having the three-layer structure constituting the solar cell surface protective sheet of the present invention, it is particularly preferable that the fluorine-free resin sheet (C) is a PC sheet, and also constitutes the fluorine resin film (A). The fluororesin is preferably PCTFE, ETFE or FEP, and the adhesive constituting the adhesive layer (B) is preferably EVA or PVB.

上述の本発明の積層体からなる建材シートもまた、本発明の一つである。
本発明の建材シートを構成する上記本発明の積層体としては、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）のみからなりこの順で積層されてなる３層構造の積層体であってもよいし、フッ素樹脂フィルム（Ａ）、接着剤層（Ｂ）、フッ素非含有樹脂シート（Ｃ）、接着剤層（Ｂ）及びフッ素樹脂フィルム（Ａ）がこの順に積層されてなる５層構造の積層体であってもよく、用途に応じて適宜選択することができる。 本発明の建材シートは、上記５層構造の積層体からなるものであると、両表面がフッ素樹脂からなることとなり、耐候性向上の点で、好ましい。 The building material sheet comprising the above-mentioned laminate of the present invention is also one aspect of the present invention.
The laminate of the present invention constituting the building material sheet of the present invention consists of only a fluororesin film (A), an adhesive layer (B), and a fluorine-free resin sheet (C), and is laminated in this order 3 A laminate having a layer structure may be used, and the fluororesin film (A), the adhesive layer (B), the fluorine-free resin sheet (C), the adhesive layer (B), and the fluororesin film (A) It may be a laminate having a five-layer structure laminated in order, and can be appropriately selected according to the application. If the building material sheet of the present invention is made of the laminate having the above five-layer structure, both surfaces are made of fluororesin, which is preferable in terms of improving weather resistance.

本発明の積層体は、上述の構成よりなるので、耐候性、耐久性、耐衝撃性等に優れ、軽量であるので、太陽電池表面保護シート及び建材シートとして好適に使用することができる。 Since the laminated body of this invention consists of an above-mentioned structure, since it is excellent in a weather resistance, durability, impact resistance, etc. and is lightweight, it can be used conveniently as a solar cell surface protection sheet and a building material sheet.

以下に実施例及び比較例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例及び比較例にのみに限定されるものではない。
各実施例及び各比較例における組成物の量は、特に断りがない場合は、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.
The amount of the composition in each example and each comparative example is based on mass unless otherwise specified.

各実施例及び各比較例に記載の各測定値は、以下の方法により求めた値である。
１．透明性
耐侯性テストにかける前の積層体の全光線透過率を（株）東洋精機製作所製のヘイズガードＩＩを使用して測定し、積層体の透明性とした。
２．促進耐侯試験
（１）フッ素樹脂表面側からスーパーＵＶテスターＷ１３（商品名：岩崎電気（株）製の耐侯性試験機）を用いて、促進耐侯試験を１０００時間行った。
試験条件は、照射１２時間（照度：１００ｍＷ／ｃｍ２、ブラックパネル温度：６３℃、相対湿度：７０％）、結露（照度：０ｍＷ／ｃｍ２、照射ブラックパネル温度：室温、相対湿度：１００％）とした。
（２）促進耐侯試験後の積層体の光透過率、黄変度〔ΔＹＩ〕、紫外線照射前からの引張強度の低下率を下記方法で測定し、耐侯性とした。
（光透過率）
（株）東洋精機製作所製のヘイズガードＩＩを使用し、ＡＳＴＭ Ｄ １００３に基づいて測定した。
（黄変度〔ΔＹＩ〕）
スガ試験機（株）製のＳＭカラーコンピューターを使用し、ＪＩＳ Ｚ ８７２２ 条件ｄに準拠して測定した。
（引張強度）
（株）オリエンテック製の万能材料試験機ＲＴＣ−１２２５Ａを使用し、ＡＳＴＭ Ｄ８８２に基づいて測定した。
３．剥離試験（耐熱水試験）
作成した積層体を９０℃の熱水に９６時間浸漬後、（株）オリエンテック製の万能材料試験機ＲＴＣ−１２２５Ａを使用し、ＪＩＳ Ｋ ６８５４に基づいて、フッ素樹脂フィルム（Ａ）とフッ素非含有樹脂シート（Ｃ）との間の剥離強度を測定した。 Each measured value described in each example and each comparative example is a value obtained by the following method.
1. The total light transmittance of the laminate before being subjected to the transparency weather resistance test was measured using a haze guard II manufactured by Toyo Seiki Seisakusho Co., Ltd., and the transparency of the laminate was determined.
2. Accelerated weather resistance test (1) The accelerated weather resistance test was conducted for 1000 hours from the fluororesin surface side using a super UV tester W13 (trade name: weather resistance tester manufactured by Iwasaki Electric Co., Ltd.).
Test conditions were irradiation for 12 hours (illuminance: 100 mW / cm 2 , black panel temperature: 63 ° C., relative humidity: 70%), condensation (illuminance: 0 mW / cm 2 , irradiation black panel temperature: room temperature, relative humidity: 100%). ).
(2) The light transmittance, yellowing degree [ΔYI] of the laminate after the accelerated weathering test, and the rate of decrease in tensile strength from before ultraviolet irradiation were measured by the following methods to obtain weatherability.
(Light transmittance)
Using a haze guard II manufactured by Toyo Seiki Seisakusho Co., Ltd., measurement was performed based on ASTM D 1003.
(Yellowness [ΔYI])
An SM color computer manufactured by Suga Test Instruments Co., Ltd. was used, and measurement was performed in accordance with JIS Z 8722 condition d.
(Tensile strength)
A universal material testing machine RTC-1225A manufactured by Orientec Co., Ltd. was used, and measurement was performed based on ASTM D882.
3. Peel test (heat resistant water test)
The prepared laminate is immersed in hot water at 90 ° C. for 96 hours, and then a universal material testing machine RTC-1225A manufactured by Orientec Co., Ltd. is used. Based on JIS K 6854, the fluororesin film (A) and fluorine The peel strength between the containing resin sheet (C) was measured.

実施例１
エチレン／テトラフルオロエチレン共重合体〔ＥＴＦＥ〕フィルム（厚さ０．０５ｍｍ、ダイキン工業社製）の片面、及び、ポリカーボネート〔ＰＣ〕シート（三菱エンジニアリングプラスチック（株）製のユーピロンフィルムＥＦ−２０００（商品名）、厚さ０．１ｍｍ）の片面を、特開昭５９−２１７７３１号公報（実施例４）記載と同様の方法でＡｒとＨ２の混合ガス（Ａｒ：Ｈ２＝９０：１０、体積比）雰囲気下でプラズマ処理した。
接着剤層（Ｂ）として、エチレン／酢酸ビニル共重合体〔ＥＶＡ〕（商品名：ソーラーエバ、三井化学ファブロ（株）製、厚さ０．４ｍｍ）を、上記ＥＴＦＥフィルムの処理面とＰＣシートの処理面の間に挟むようにして重ね、真空加熱圧着式のラミネーター（ミカドテクノス社製）を用いて１５０℃で３０分間加熱することにより積層体を作製した（図１）。 Example 1
One side of ethylene / tetrafluoroethylene copolymer [ETFE] film (thickness 0.05 mm, manufactured by Daikin Industries) and polycarbonate [PC] sheet (Iupilon film EF-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) Name) and a thickness of 0.1 mm), a mixed gas of Ar and H 2 (Ar: H 2 = 90: 10, volume) in the same manner as described in JP-A-59-217731 (Example 4) Ratio) Plasma treatment was performed under an atmosphere.
As the adhesive layer (B), an ethylene / vinyl acetate copolymer [EVA] (trade name: Solar Eva, manufactured by Mitsui Chemicals, Inc., thickness 0.4 mm), the treated surface of the ETFE film and the PC sheet The laminate was prepared by sandwiching between the treated surfaces and heating at 150 ° C. for 30 minutes using a vacuum thermocompression laminator (manufactured by Mikado Technos) (FIG. 1).

実施例２
上記ＥＴＦＥフィルムのプラズマ処理を、特開平４−３４９６７２号公報（試作例１）記載と同様の方法で、圧力３０Ｐａ、処理強度５０Ｗ・秒／ｃｍ２にて、ＮＨ３ガスをプラズマ発生源として行う以外は、実施例１と同様にして積層体を得た（図１）。 Example 2
Plasma treatment of the ETFE film is performed in the same manner as described in JP-A-4-349672 (Prototype Example 1) at a pressure of 30 Pa and a treatment intensity of 50 W · sec / cm 2 using NH 3 gas as a plasma generation source. Except for this, a laminate was obtained in the same manner as in Example 1 (FIG. 1).

実施例３
上記ＰＣシートについてプラズマ処理を行わなかった以外は、実施例１と同様にして積層体を得た（図１）。 Example 3
A laminate was obtained in the same manner as in Example 1 except that the PC sheet was not subjected to plasma treatment (FIG. 1).

実施例４〜５
ＥＴＦＥフィルムに代えてＦＥＰフィルム（厚さ０．０５ｍｍ、ダイキン工業社製）を用いた以外は、実施例１〜２と同様にして積層体を得た（図１）。 Examples 4-5
A laminate was obtained in the same manner as in Examples 1 and 2 except that an FEP film (thickness 0.05 mm, manufactured by Daikin Industries, Ltd.) was used instead of the ETFE film (FIG. 1).

実施例６
ＥＴＦＥフィルムについて、特開昭５９−２１７７３１号公報（比較例４）記載の方法でＡｒガス雰囲気にて片面をプラズマ処理した以外は、実施例１と同様にして積層体を得た（図１）。 Example 6
For the ETFE film, a laminate was obtained in the same manner as in Example 1 except that one side was plasma-treated in an Ar gas atmosphere by the method described in JP-A-59-217731 (Comparative Example 4) (FIG. 1). .

実施例７
ＰＣシートの片面に、特開昭５９−２１７７３１号公報（実施例４）記載の方法でＡｒとＨ２の混合ガス（Ａｒ：Ｈ２＝９０：１０、体積比）雰囲気下でプラズマ処理した。
上記ＰＣシートの処理面に、ポリビニルブチラール（積水化学（株）製エスレックＢＭ−１）をイソプロピルアルコール〔ＩＰＡ〕に該ＩＰＡの１０質量％となるよう溶解したものに、紫外線吸収剤（チバ・スペシャル・ケミカルズ（株）製チバチヌビン４７７ＤＷ）をポリビニルブチラールの４質量％となるよう添加した接着剤塗工液を、フィルムアプリケーター（商品名：（株）安田精機製作所製）を用いて、乾燥後の厚みが０．０１５ｍｍとなるよう塗布し、乾燥させた。同様に、実施例１に記載の方法で表面処理したＥＴＦＥフィルムの処理面側にも、上記接着剤塗工液を、フィルムアプリケーター（商品名：（株）安田精機製作所製）を用いて、乾燥後の厚みが０．０１５ｍｍとなるよう塗布し、乾燥させた。接着剤塗布面同士を張り合わせ、真空加熱圧着式のラミネーターを用いて、１７０℃で１時間加熱することにより積層体を作製した（図２）。 Example 7
One side of the PC sheet was plasma-treated in an atmosphere of a mixed gas of Ar and H 2 (Ar: H 2 = 90: 10, volume ratio) by the method described in JP-A-59-217731 (Example 4).
To the treated surface of the PC sheet, polyvinyl butyral (Surekku Chemical Co., Ltd., ESREC BM-1) was dissolved in isopropyl alcohol [IPA] so as to be 10% by mass of the IPA. -Thickness after drying using a film applicator (trade name: manufactured by Yasuda Seiki Seisakusyo Co., Ltd.) using an adhesive coating solution to which Cibachinubin 477DW (Chemicals Co., Ltd.) is added to 4% by mass of polyvinyl butyral. Was applied to a thickness of 0.015 mm and dried. Similarly, the adhesive coating liquid is also dried on the treated surface side of the ETFE film surface-treated by the method described in Example 1, using a film applicator (trade name: manufactured by Yasuda Seiki Seisakusho). It apply | coated so that latter thickness might be set to 0.015 mm, and it was made to dry. Adhesive application surfaces were bonded together, and a laminate was prepared by heating at 170 ° C. for 1 hour using a vacuum thermocompression laminator (FIG. 2).

実施例８
ＡｒとＨ２の混合ガスの代わりにＮＨ３ガスを用いること以外は、実施例７と同様にして積層体を得た（図２）。 Example 8
A laminate was obtained in the same manner as in Example 7 except that NH 3 gas was used instead of the mixed gas of Ar and H 2 (FIG. 2).

比較例１
ＥＴＦＥフィルムの片面について、プラズマ処理に代え、空気中にて１．５Ｗ・秒／ｃｍ２の条件でコロナ処理を行う以外は、実施例１と同様にして積層体を得た（図１）。 Comparative Example 1
On one side of the ETFE film, a laminate was obtained in the same manner as in Example 1 except that instead of plasma treatment, corona treatment was performed in air under the condition of 1.5 W · sec / cm 2 (FIG. 1).

比較例２
ＥＴＦＥフィルムの片面のプラズマ処理を、Ｏ２ガスをプラズマ発生源として行う以外は実施例１と同様にして積層体を得た（図１）。 Comparative Example 2
A laminate was obtained in the same manner as in Example 1 except that plasma treatment on one side of the ETFE film was performed using O 2 gas as a plasma generation source (FIG. 1).

比較例３
ＥＴＦＥフィルムの代りにＦＥＰフィルム（厚さ０．０５ｍｍ、ダイキン工業社製）を用いる以外は、比較例２と同様にして積層体を得た（図１）。 Comparative Example 3
A laminate was obtained in the same manner as in Comparative Example 2 except that an FEP film (thickness 0.05 mm, manufactured by Daikin Industries, Ltd.) was used instead of the ETFE film (FIG. 1).

比較例４
ＰＣシートをプラズマ処理せずに用いた以外は、実施例７と同様にして積層を行ったが、該ＰＣシートと接着剤層との間を接着することができなかった（図２）。 Comparative Example 4
Lamination was performed in the same manner as in Example 7 except that the PC sheet was used without being subjected to plasma treatment, but the PC sheet and the adhesive layer could not be adhered (FIG. 2).

比較例５
ＥＴＦＥフィルムのプラズマ処理をＡｒとＨ２の混合ガスに代えＯ２ガスをプラズマ発生源として行う以外は、実施例７と同様にして積層を行ったが、該ＥＴＦＥフィルムと接着剤層との間を接着することができなかった（図２）。 Comparative Example 5
Lamination was performed in the same manner as in Example 7 except that the plasma treatment of the ETFE film was replaced with a mixed gas of Ar and H 2 and O 2 gas was used as a plasma generation source, but the lamination was performed between the ETFE film and the adhesive layer. Could not be adhered (FIG. 2).

比較例６
紫外線吸収剤（チバチヌビン４７７ＤＷ）を添加せずエスレックＢＭ−１溶液を調製したものを接着剤層（Ｂ）の材料とする以外は、実施例７と同様にして積層体を得た（図２）。 Comparative Example 6
A laminate was obtained in the same manner as in Example 7 except that the material for the ESREC BM-1 solution was prepared without adding the ultraviolet absorber (Cibachinubin 477DW) (FIG. 2). .

各実施例及び各比較例の構成を表１に、結果を表２に示す。 Table 1 shows the configuration of each example and each comparative example, and Table 2 shows the results.

Figure 2009137012
Figure 2009137012

Figure 2009137012
Figure 2009137012

本発明の積層体は、上述の構成よりなるので、耐候性、耐久性、耐衝撃性等に優れ、軽量であるので、太陽電池表面保護シート及び建材シートとして好適に使用することができる。 Since the laminated body of this invention consists of an above-mentioned structure, since it is excellent in a weather resistance, durability, impact resistance, etc. and is lightweight, it can be used conveniently as a solar cell surface protection sheet and a building material sheet.

実施例１〜６及び比較例１〜３の各積層体の模式図である。It is a schematic diagram of each laminated body of Examples 1-6 and Comparative Examples 1-3. 実施例７〜８並びに比較例４〜６の各積層体の模式図である。It is a schematic diagram of each laminated body of Examples 7-8 and Comparative Examples 4-6.

符号の説明Explanation of symbols

１．フッ素樹脂フィルム（Ａ）
２．接着剤層（Ｂ）
３．フッ素非含有樹脂シート（Ｃ）
４（ａ）．フッ素樹脂フィルム（Ａ）側に設けた接着剤層（Ｂ）
４（ｂ）．フッ素非含有樹脂シート（Ｃ）側に設けた接着剤層（Ｂ） 1. Fluoropolymer film (A)
2. Adhesive layer (B)
3. Fluorine-free resin sheet (C)
4 (a). Adhesive layer (B) provided on the fluororesin film (A) side
4 (b). Adhesive layer (B) provided on the fluorine-free resin sheet (C) side

Claims (6)

フッ素樹脂フィルム（Ａ）、紫外線吸収剤を含む接着剤層（Ｂ）及びフッ素非含有樹脂シート（Ｃ）がこの順で積層されてなり全光線透過率が８５％以上である
ことを特徴とする積層体。 A fluororesin film (A), an adhesive layer (B) containing an ultraviolet absorber, and a fluorine-free resin sheet (C) are laminated in this order, and the total light transmittance is 85% or more. Laminated body. フッ素樹脂フィルム（Ａ）を構成するフッ素樹脂ポリマーがエチレン／テトラフルオロエチレン共重合体、ポリクロロトリフルオロエチレン及びテトラフルオロエチレン／ヘキサフルオロプロピレン共重合体よりなる群から選ばれる少なくとも１つである請求項１記載の積層体。 The fluororesin polymer constituting the fluororesin film (A) is at least one selected from the group consisting of an ethylene / tetrafluoroethylene copolymer, a polychlorotrifluoroethylene, and a tetrafluoroethylene / hexafluoropropylene copolymer. Item 2. The laminate according to Item 1. 接着剤層（Ｂ）を構成する接着剤がエチレン／酢酸ビニル共重合体、ポリビニルアセタール樹脂及びシリコーン樹脂よりなる群から選ばれる少なくとも１つである請求項１又は２記載の積層体。 The laminate according to claim 1 or 2, wherein the adhesive constituting the adhesive layer (B) is at least one selected from the group consisting of an ethylene / vinyl acetate copolymer, a polyvinyl acetal resin, and a silicone resin. フッ素非含有樹脂シート（Ｃ）を構成するフッ素非含有樹脂がポリカーボネート樹脂である請求項１〜３の何れか記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the fluorine-free resin constituting the fluorine-free resin sheet (C) is a polycarbonate resin. 請求項１〜４の何れか１項に記載の積層体からなる
ことを特徴とする太陽電池表面保護シート。 It consists of a laminated body of any one of Claims 1-4, The solar cell surface protection sheet characterized by the above-mentioned. 請求項１〜４の何れか１項に記載の積層体からなる
ことを特徴とする建材シート。 A building material sheet comprising the laminate according to any one of claims 1 to 4.
JP2006086174A 2006-03-27 2006-03-27 Laminate, sheet for protecting surface of solar battery, and building material sheet Pending JP2009137012A (en)

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