JP5571582B2 - 太陽電池用3層フィルム - Google Patents
太陽電池用3層フィルム Download PDFInfo
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- JP5571582B2 JP5571582B2 JP2010545536A JP2010545536A JP5571582B2 JP 5571582 B2 JP5571582 B2 JP 5571582B2 JP 2010545536 A JP2010545536 A JP 2010545536A JP 2010545536 A JP2010545536 A JP 2010545536A JP 5571582 B2 JP5571582 B2 JP 5571582B2
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Classifications
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- 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
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- H—ELECTRICITY
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Description
さらに、熱膨張、特に電池組み立て中の収縮を防ぐために、フィルムは容積が熱的に安定していなければならない。太陽電池の組み立て作業では各層が溶剤ベースの添加剤を用いて結合され、次いでラミネート加工される。添加剤中に溶剤を用いることによって上記溶剤をフィルムに浸透させることができる。電池の組み立て作業は必要に応じてコロナ型の表面酸化処理を用いて高温(>130℃)で行なわれる。コロナ型の表面酸化処理をすると、黄変およびフルオロポリマーの機械特性の劣化が起こる。
本発明のさらに他の対象は、リヤパネルが上記多層フィルムで被覆されている太陽電池にある。
第1層、第2層、第3層は0.1〜100重量%の一種以上のフルオロポリマー、好ましくはVDFのホモポリマーまたはコポリマーを含むのが有利である。
(1)100%のVDFのホモポリマーまたはコポリマーを含む組成物Aの第1層、
(2)30〜75重量部のVDFのホモポリマーまたはコポリマーと、10〜45部のMMAのホモポリマーまたはコポリマーと、10〜25部の少なくとも一種の無機充填剤とを含む組成物Bの第2層(合計で100重量部)、
(3)100%のVDFのホモポリマーまたはコポリマーを含む組成物Cの第3層。
本発明の「部」とは重量部を意味する。
組成物AとCの各層の厚さはそれぞれ別々に1〜30μm、有利には2〜20μm、好ましくは3〜18μm、さらに好ましくは5〜15μmにすることができる。
本発明の一つの変形例では、組成物AとCの層の厚さは同一である。
本発明の別の変形例では、第1層と第3層の組成物Aおよび組成物Cは同一である。
組成物Bの層の厚さは4〜45μm、有利には5〜40μm、好ましくは7〜30μm、さらに好ましくは10〜25μmである。
X1はHまたはFを表し、
X2およびX3はH、F、Cl、式CnFmHp-のフルオロアルキル基またはフルオロアルコキシ基CnFmHpO-を表し、nは1〜10の整数、mは1〜(2n+1)の整数であり、pは2n+1−mに等しい)
(1)TFEのホモポリマーまたはコポリマー、特にPTFE(ポリテトラフルオロエチレン)、ETFE(エチレン/テトラフルオロエチレンコポリマー)および下記のコポリマー:TFE/PMVE(テトラフルオロエチレン/ペルフルオロ(メチルビニルエーテル)コポリマー)、TFE/PEVE(テトラフルオロエチレン/ペルフルオロ(エチルビニルエーテル)コポリマー)、TFE/PPVE(テトラフルオロエチレン/ペルフルオロ(プロピルビニルエーテル)コポリマー)およびE/TFE/HFP(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ターポリマー)
(2)VDFのホモポリマーまたはコポリマー、特にPVDFおよびVDF/HFPコポリマー、および、
(3)CTFEのホモポリマーまたはコポリマー、特に、PCTFE(ポリクロロトリフルオロエチレン)およびE/CTFE(エチレン/クロロトリフルオロエチレンコポリマー)。
VDFと共重合可能なフルオロコモノマーは例えば下記の中から選択するのが有利である:フッ化ビニル、トリフルオロエチレン(VF3);クロロトリフルオロエチレン(CTFE);1,2-ジフルオロエチレン;テトラフルオロエチレン(TFE);ヘキサフルオロプロピレン(HFP);ペルフルオロ(メチルビニルエーテル)(PMVE)、ペルフルオロ(エチルビニルエーテル)(PEVE)およびペルフルオロ(プロピルビニルエーテル)(PPVE)等のペルフルオロ(アルキルビニルエーテル);ペルフルオロ(1,3-ジオキソール);ペルフルオロ(2,2-ジメチル-1,3-ジオキソール)(PDD)およびこれらの混合物。
HFPはVDFと良く共重合し、優れた熱機械的特性を与えるので、コモノマーはHFPであるのが有利である。コポリマーはVDFとHFPのみを含むのが好ましい。
本発明の別の変形例では、組成物Aおよび組成物CはPVDFホモポリマーから成る。
アルケマ社の製品カイナー(登録商標)が特に望ましく、例えば、融点が140℃以上、好ましくは300℃以下である、15重量%以下、有利には13重量%以下、好ましくは11重量%以下、さらに好ましくは少なくとも10重量%のコモノマーを含むカイナー(登録商標)700系の製品(VDFホモポリマー)またはカイナーフレックス(登録商標)製品の一部(VDFコポリマー)が好ましい。
この組成物Bの層は機能層ともよばれ、紫外線および可視光に対して不透明である。「不透明(opaque)」とは所定厚さでの紫外線および可視光の透過率が、層Bの組成物中に「充填剤」、特に無機充填剤を全く含まないA/B/C型の構造物と比較して、一定の値またはパーセンテージたけ低いということを意味する。本発明のA/B/C構造物は温度に対する寸法収縮性が従来技術の構造物と比べて大きく優れ、組成物AとCの層は、充填剤、例えば無機充填剤と、酸素と、温度との複合作用によって、または、無機充填剤の存在下でのコロナ型の表面酸化処理の作用によって、層Bのフルオロポリマーの分解を防止することができる。
MMAと共重合可能なコモノマーの例としてはアルキル(メタ)アクリレート、アクリロニトリル、ブタジエン、スチレンおよびイソプレン等が挙げられる。アルキル(メタ)アクリレートの例は下記文献に記載されている。
カークオスマ(Kirk-Othmer)化学技術百科辞典、第4版、第1巻、第292〜293頁および第16巻、第475〜478頁
MMAポリマーの230℃、3.8kgの荷重下で測定したMVI(メルトボリュームインデックス)は2〜15cm3/10分にすることができる。
組成物B中のMMAポリマーの含有率は1〜55重量%、有利には5〜50重量%、好ましくは10〜45重量%、さらに好ましくは20〜40重量%である。
無機充填剤が別の機能を有することもできる。例えば、無機充填剤は難燃機能、例えば酸化アンチモン(Sb2O3、Sb2O5)、Al(OH)3、Mg(OH)2、ハンタイト(3MgCO3・CaCO3)、ハイドロマグネサイト(3MgCO3・Mg(OH)2・3H2O)のような難燃機能を有することができる。無機充填剤を導電性充填剤(例えば、カーボンブラックまたはカーボンナノチューブ)にすることもできる。
組成物AおよびCの各層の厚さはそれぞれ独立して1〜30μm、有利には2〜20μm、好ましくは3〜18μm、さらに好ましくは5〜15μmにすることができる。
本発明の一つの変形例では、組成物AとCの層の厚さは同一である。
本発明の別の変形例では、第1層と第3層の組成物Aおよび組成物Cが同一である。
組成物Bの層の厚さは4〜45μm、有利には5〜40μm、好ましくは7〜30μm、さらに好ましくは10〜25μmである。
A/B/A型の構造物とは2つの層Aが同じ厚さを有することを意味するものではない。
フルオロポリマーをベースにしたフィルム、特にVDFのホモポリマーまたはコポリマーをベースにしたフィルムは共押出技術、例えばブロー成形によって製造するのが好ましいが、注型法、溶剤法または被覆 (plaxage) 法を用いることもできる。
以下、上記のフルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにしたフィルムの用途を詳細に説明する。
太陽電池の裏面保護フィルム
太陽電池の裏面を上記フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにしたフィルムで保護することができる。太陽電池は光エネルギーを電流に変換する。一般に、太陽電池は電気的接続手段によって互いに直列に接続された太陽電池セルから成る。これらの太陽電池セルは珪素溶融中にホウ素をPドープし、照明表面にリンをNドープした多結晶シリコンから製造される一般に単一接合の電池セルで、この電池セルを積層体中に配置する。この積層体はシリコンを酸化および湿気から保護するために太陽電池セルを被覆するEVA(エチレン/酢酸ビニルコポリマー)から成る。積層体は片側の支持体の役目をするガラス板と反対側のフィルムとの間に固定されて、太陽電池モジュールは老化(紫外線、塩霧等)、引掻き、湿気または水蒸気から保護される。
150℃でのフィルムの体積収縮は2%以下、有利には1.5%以下、好ましくは1%以下、さらに好ましくは0.5%以下にする。
組み立てた太陽電池の裏面に位置する組成物AまたはCから成る層は層Bより高い耐薬品性および耐紫外線老化性を付与する。
(1)100重量%のVDFのホモポリマーまたはコポリマーを含む組成物Aの第1層、
(2)30〜75部の少なくとも一種のVDFのホモポリマーまたはコポリマーと、5〜45部の少なくとも一種のMMAのホモポリマーまたはコポリマーと、10〜30部の少なくとも一種の無機充填剤(合計で100部)とを含む組成物Bの第2層、
(3)100重量%のVDFのホモポリマーまたはコポリマーを含む組成物Cの第3層。
PVDFフィルム/接着剤/PET/接着剤/PVDFフィルム
用いる接着剤の例としてはメチルエチルケトン(MEK)またはトルエンを含むポリエステルまたはポリウレタン配合物が挙げられる。
フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにした上記フィルムは可撓性基材、例えばテクニカルテクスチャー(工業布)(PVC、ガラス繊維、グラスマット、アラミド、ケブラー等)の保護に用いることもできる。PVC可撓性基材の例としてはPVC防水シートがある。フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにした上記フィルムは積層技術を用いて接着層を介して積層できる。
フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにした組成物Aが2層存在することによって、積層中の組成物Bの層の劣化(分解)が防止され、最終構造物の耐薬品性および耐紫外線老化性が高くなる。
フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにした上記フィルムは、金属基材、例えば鋼、銅またはアルミニウム等の保護に用いることもできる。フルオロポリマー、特にVDFのホモポリマーまたはコポリマーをベースにしたフィルムは積層技術を用いて接着層を介して積層できる。
紫外線不透明度:
紫外線不透明度は分光光度計を用いて紫外線スペクトル領域内の透過吸光測定で評価した。
ASTM D1003規格による透過率:
可視領域内の透過率測定はASTM D1003規格に従ってD65光源および角度2°で分光光度計を用いて行った。透過率値は400〜740nmのスペクトル領域の平均値に対応する。
EN 438−2:2000規格に従って行った。この方法では2〜3滴のメチルエチルケトンを室温でフィルム上に塗布し、時計皿で16時間、覆った。次いで、時計皿を外し、石鹸水で洗浄した後、脱イオン水で洗浄した。1時間後に清浄度を調べた。フィルムは下記の評価尺度に従って等級分けした:
レベル5:目に見える変化なし
レベル4:ある角度でのみ見える光沢および/または色の小さな変化
レベル3:光沢および/または色の中程度の変化
レベル2:光沢および/または色の大きな変化
レベル1:表面劣化および/またはブリスター形成。
ISO 11357−3規格に従って行う。得られたサーモグラムピークは、構造物の層の各組成物の融点Tmを示している。これは耐熱性の指標とみなされる。
収縮
ISO 11501規格に従って測定した。10cm×10cmの正方形が描かれた12×12cm2の正方形フィルム片を150℃の換気オーブンに10分間入れた。次いで、枠の寸法を再測定した。初期寸法に対する各寸法の変化によって収縮を評価した。保持した値は最大値である。
PVDF−1:
顆粒の形をしたPVDFのホモポリマーで、MFI(メルトフローインデックス)は10g/10分(230℃/12.5kg)、230℃/100s-1での粘度は1900mPa.s、融点は165℃である。
PVDF−2:
顆粒の形をしたVDF/HFPコポリマー(11重量%のHFP)で、MFIは5g/10分(230℃/12.5kg)、230℃/100s-1での粘度は2500mPa.s、融点は142℃である。
PVDF−3:
顆粒の形をしたVDF/HFP不均一コポリマー(10重量%のHFP)で、MFIは5g/10分(230℃/12.5kg)、230℃/100s-1での粘度は2300mPa.s、融点は163℃である。
PVDF−4:
顆粒の形をしたVDF/HFPコポリマー(17重量%のHFP)で、MFIは10g/10分(230℃/12.5kg)、230℃/100s-1での粘度は2200mPa.s、融点は135℃である。
PMMA:
Altuglas International社の真珠形製品であるオログラス(OROGLAS、登録商標)BS-8で、MFIは4.5g/10分(230℃/3.8kg)、コモノマーのメチルアクリレートを6重量%含む。このPMMAは衝撃改質剤を含んでいない。
TiO 2 :
デュポン社の製品であるTi-Pure(登録商標)R 960二酸化チタンを用いた。メーカ供給時の平均粒径は0.5μm。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−2と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−1と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−3と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)50重量%のPVDF−3と、30重量%のPMMAと、20重量%のTiO2とを含む15μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)40重量%のPVDF−3と、36重量%のPMMAと、24重量%のTiO2とを含む15μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)40重量%のPVDF−3と、36重量%のPMMAと、24重量%のTiO2とを含む20μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む8μm厚さの層、
(2)60重量%のPVDF−3と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)100重量%のPVDF−1を含む8μm厚さの層。
下記構成の2層フィルムの構成:
(1)100%のPVDF−1を含む10μm厚さの層、
(2)60重量%のPVDF−2と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層。
下記構成のA/B/C3層フィルム:
(1)100%のPVDF−1を含む10μm厚さの層、
(2)60重量%のPVDF−2と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)30重量%のPVDF−2と、70重量%のPMMAとを含む5μm厚さの層。
下記構成のA/B/C3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−2と、24重量%のPMMAと、16重量%のTiO2とを含む20μm厚さの層、
(3)100%のPVDF−4を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−3と、24重量%のPMMAと、16重量%のTiO2とを含む30μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
下記構成のA/B/A3層フィルム:
(1)100%のPVDF−1を含む5μm厚さの層、
(2)60重量%のPVDF−3と、24重量%のPMMAと、16重量%のTiO2とを含む10μm厚さの層、
(3)100重量%のPVDF−1を含む5μm厚さの層。
第1層の組成物Aが第3層の組成物Cと同一な場合、耐熱性は組成物Aのみで示す。
Claims (10)
- フルオロポリマーを含む組成物Aの第1層と、充填されたフルオロポリマーを含む組成物Bの第2層と、フルオロポリマーを含む組成物Cの第3層とを有するA/B/C構造の多層フィルムにおいて、
第1層と第3層のDSCで測定した融点は150℃以上であり、25μm厚さの多層フィルムの場合の可視光透過率が25%以下であり、
組成物Aの層は100重量%のVDFのホモポリマーから成り、
組成物Cの層は100重量%のVDFのホモポリマーから成り、
組成物Bの層は30〜75重量部のVDFのホモポリマーまたはコポリマーと、5〜45重量部のMMAのホモポリマーまたはコポリマーと、10〜30重量部の少なくとも一種の無機充填剤とから成り(合計で100重量部)、
組成物AおよびCの各層の厚さはそれぞれ独立して5〜15μmであり、
組成物Bの層の厚さは5〜40μmである、
ることを特徴とする多層フィルム。 - 150℃でのフィルムの体積収縮が1%以下である請求項1に記載の多層フィルム。
- 第2層のフルオロポリマーが15重量%以下のコモノマーを含む請求項1または2に記載の多層フィルム。
- 第2層のフルオロポリマーのDSCで測定した融点が140℃以上である請求項1〜3のいずれか一項に記載の多層フィルム。
- 第2層の充填剤がTiO2、炭酸カルシウム、シリカ、石英、アルミナ、タルクおよび雲母の中から選択される少なくとも一種の充填剤を含む請求項1〜4のいずれか一項に記載の多層フィルム。
- 組成物B中の充填剤の含有率が10〜27重量%である請求項1〜5のいずれか一項に記載の多層フィルム。
- 組成物B中の充填剤の含有率が15〜25重量%である請求項6に記載の多層フィルム。
- 第2層のフルオロポリマーがVDFのコポリマーである請求項1〜7のいずれか一項に記載の多層フィルム。
- 請求項1〜8のいずれか一項に記載の多層フィルムの太陽電池での使用。
- 請求項1〜8のいずれか一項に記載の多層フィルムを組立電池のリヤパネル内に含む太陽電池。
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FR0850756A FR2927016B1 (fr) | 2008-02-06 | 2008-02-06 | Film tricouche pour cellule photovoltaique |
US4322908P | 2008-04-08 | 2008-04-08 | |
US61/043,229 | 2008-04-08 | ||
PCT/FR2009/050190 WO2009101343A1 (fr) | 2008-02-06 | 2009-02-06 | Film tricouche pour cellule photovoltaïque |
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AT (1) | ATE525205T1 (ja) |
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DE102009001629A1 (de) * | 2009-03-18 | 2010-09-23 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit hoher Strahlungstransmission |
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CN101932443A (zh) | 2010-12-29 |
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EP2237950A1 (fr) | 2010-10-13 |
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WO2009101343A1 (fr) | 2009-08-20 |
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