JP5844253B2 - 溶媒含有ポリカーボネート溶液を脱気する装置および方法 - Google Patents
溶媒含有ポリカーボネート溶液を脱気する装置および方法 Download PDFInfo
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- JP5844253B2 JP5844253B2 JP2012512253A JP2012512253A JP5844253B2 JP 5844253 B2 JP5844253 B2 JP 5844253B2 JP 2012512253 A JP2012512253 A JP 2012512253A JP 2012512253 A JP2012512253 A JP 2012512253A JP 5844253 B2 JP5844253 B2 JP 5844253B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0005—Degasification of liquids with one or more auxiliary substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0042—Degasification of liquids modifying the liquid flow
- B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
- B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0008—Anti-static agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0026—Flame proofing or flame retarding agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0032—Pigments, colouring agents or opacifiyng agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0038—Plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0047—Agents changing thermal characteristics
- B29K2105/005—Heat sensitisers or absorbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
フラッシュ脱蔵器の分離器中の絶対圧は、0.3〜6bar、好ましくは0.5〜4bar、より好ましくは1〜2barの間である。
65重量%のポリカーボネートと、33.5重量%のクロロベンゼンと、1.5重量%の塩化メチレンから成る溶液から、本発明に係る装置を用いて、6.5t/時のポリカーボネートを単離した。使用されるベント式押出機は、密接噛合型の、コロタトリー(corotatory)2軸押出機として設計され、178mmのスクリュー径を有し、直径に対する押出機の長さの比が48であり、流入領域と脱蔵領域において2つのフライト構造が構成される。フラッシュ脱蔵器は、底部に穴が設けられた、直径150mmのパイプから構成された。フラッシュ脱蔵器内の入り口温度は230℃であった。共留剤領域において、13kg/時の窒素が供給された。単離したポリカーボネートは、1.295の相対粘度を有した。
65重量%のポリカーボネートと、33.5重量%のクロロベンゼンと、1.5重量%の塩化メチレンから成る溶液から、押出機を用いる後脱蔵法により、6.5t/時のポリカーボネートを単離した。使用したベント式押出機は、本発明の実施例に類似し、密接噛合型の、コロタトリー(corotatory)2軸押出機として設計され、178mmのスクリュー径を有し、直径に対する押出機の長さの比が48であり、流入領域と脱蔵領域において2つのフライト構造が構成される。共留剤領域において、本発明に係る実施例と同じ、13kg/時の窒素が供給された。後脱蔵前のポリマー溶液の温度は185℃であった。押出機内への流入はバルブを介しておこなった。単離したポリカーボネートは、1.295の相対粘度を有した。
2 シェルアンドチューブ熱交換器
5 生成物分配器(図2挿入チューブ)
6 ノズル板(図2オリフィス)
7 分離容器
8 蒸気ライン
9 流入領域
10 予備領域
11 脱蔵領域
12 脱蔵ドーム
13 添加位置
14 供給ライン
15 添加位置
16 圧力増加および混合領域
20 フラッシュチューブ
21 分離器
22 蒸気ライン
23 円錐部
24 押出ハウジング
25 押出軸
Claims (14)
- 溶媒含有ポリカーボネート溶融体を脱蔵する装置であって、フラッシュ脱蔵器がベント式押出機と併用され、該フラッシュ脱蔵器が、該押出機の上方に直接配置され、該フラッシュ脱蔵器の流入要素が、上流生成物分配器を備える分配板形態であるか、またはオリフィスを備えるパイプ形態であることを特徴とする、該装置。
- 蒸気ラインがフラッシュ脱蔵器に装着されることを特徴とする、請求項1に記載の装置。
- フラッシュ脱蔵器が、凝縮蒸気、凝縮有機熱媒体または液体有機熱媒体を用いて加熱されることを特徴とする、請求項1または2に記載の装置。
- フラッシュ脱蔵器とベント式押出機の組合せの上流に、少なくとも1種の更なるフラッシュ脱蔵器が先行することを特徴とする、請求項1から3のいずれかに記載の装置。
- ベント式押出機が2軸型または4軸型であることを特徴とする、請求項1から4のいずれかに記載の装置。
- ベント式押出機が、密接噛合型の、コロタトリー2軸押出機であることを特徴とする、
請求項1から5のいずれかに記載の装置。 - 押出機が、運搬方向に複数の脱蔵領域を有することを特徴とする、請求項1から6のいずれかに記載の装置。
- 少なくとも1種の有機溶媒と少なくとも1種のポリカーボネートを含有するポリカーボネート溶液が界面法によって調製され、第2工程において、このポリカーボネート溶液が、ベント式押出機を併用するフラッシュ脱蔵器へ供給され、該フラッシュ脱蔵器は、該ポリマー溶液が該ベント式押出機内へ直接落下するように該押出機の上に直接配置されることを特徴とする、請求項1から7のいずれかに記載の装置を用いることによるポリカーボネート溶液の脱蔵方法。
- フラッシュ脱蔵器中に形成された溶媒含有蒸気が、蒸気ラインを用いて、フラッシュ脱蔵器のハウジングから直接除去されることを特徴とする、請求項8に記載の方法。
- 共留剤としての不活性ガスが、フラッシュ脱蔵器の上流のポリマー溶融体流内へ注入および混合されることを特徴とする、請求項8または9に記載の方法。
- 不活性ガスが、ベント式押出機の1以上のハウジングにおいて、共留剤として注入されることを特徴とする、請求項8から10のいずれかに記載の方法。
- フラッシュ脱蔵器内におけるポリカーボネートの流入濃度が、60重量%〜95重量%の間であることを特徴とする、請求項8から11のいずれかに記載の方法。
- ポリマーが、フラッシュ脱蔵器に浸入する前に、熱交換器を用いて加熱されることを特徴とする請求項8から12のいずれかに記載の方法。
- 得られるポリカーボネートが、20ppm〜1000ppmの残留溶媒含有量を有することを特徴とする、請求項8から13のいずれかに記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP09007269.5 | 2009-05-30 | ||
EP09007269A EP2255860A1 (de) | 2009-05-30 | 2009-05-30 | Vorrichtung und Verfahren zum Entgasen von lösungsmittelhaltigen Polycarbonatlösungen |
PCT/EP2010/003206 WO2010139413A1 (de) | 2009-05-30 | 2010-05-26 | Vorrichtung und verfahren zum entgasen von lösungsmittelhaltigen polycarbonatlösungen |
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JP2012528896A JP2012528896A (ja) | 2012-11-15 |
JP2012528896A5 JP2012528896A5 (ja) | 2013-07-11 |
JP5844253B2 true JP5844253B2 (ja) | 2016-01-13 |
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JP2012512253A Expired - Fee Related JP5844253B2 (ja) | 2009-05-30 | 2010-05-26 | 溶媒含有ポリカーボネート溶液を脱気する装置および方法 |
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US (1) | US8497345B2 (ja) |
EP (2) | EP2255860A1 (ja) |
JP (1) | JP5844253B2 (ja) |
KR (1) | KR101743310B1 (ja) |
CN (1) | CN102448569B (ja) |
SG (1) | SG175850A1 (ja) |
WO (1) | WO2010139413A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2255859A1 (de) * | 2009-05-30 | 2010-12-01 | Bayer MaterialScience AG | Vorrichtung und Verfahren zum Entgasen von lösungshaltigen Polycarbonatlösungen |
JP5619239B1 (ja) * | 2013-08-27 | 2014-11-05 | 株式会社日本製鋼所 | ベント式二軸混練押出装置及び方法 |
CN106139626B (zh) * | 2016-08-25 | 2018-05-08 | 山东恒利热载体工程技术有限公司 | 有机热载体在线气提清除裂解轻组分的工艺及装置 |
EP3933059A1 (en) | 2020-06-29 | 2022-01-05 | Covestro Deutschland AG | Process for the preparation of a polycarbonate |
CN116507475A (zh) | 2020-11-02 | 2023-07-28 | 罗姆化学有限责任公司 | 用于二组分多相聚合物-单体材料脱气的装置及其在脱气挤出机中的用途 |
CN113694565B (zh) * | 2021-09-02 | 2023-02-21 | 上海盛普流体设备股份有限公司 | 一种具有分段式螺杆与陶瓷衬套的脱泡装置及其脱泡方法 |
WO2023198550A1 (de) | 2022-04-11 | 2023-10-19 | Covestro Deutschland Ag | Mehrwellige schneckenmaschine mit einem paar schneckenelementen mit verbesserter misch- und entgasungswirkung bei reduziertem energieeintrag |
CN115260481A (zh) * | 2022-09-05 | 2022-11-01 | 上海华峰新材料研发科技有限公司 | 一种聚合物熔体的脱挥发方法 |
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US2964513A (en) * | 1956-08-20 | 1960-12-13 | Phillips Petroleum Co | Polymer recovery process |
US3458494A (en) | 1964-07-15 | 1969-07-29 | Phillips Petroleum Co | Process for recovering olefin polymers |
US3450183A (en) * | 1964-10-02 | 1969-06-17 | Phillips Petroleum Co | Polymer recovery apparatus |
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-
2009
- 2009-05-30 EP EP09007269A patent/EP2255860A1/de not_active Withdrawn
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2010
- 2010-03-26 US US13/322,731 patent/US8497345B2/en active Active
- 2010-05-26 WO PCT/EP2010/003206 patent/WO2010139413A1/de active Application Filing
- 2010-05-26 KR KR1020117028507A patent/KR101743310B1/ko active IP Right Grant
- 2010-05-26 JP JP2012512253A patent/JP5844253B2/ja not_active Expired - Fee Related
- 2010-05-26 CN CN201080024023.6A patent/CN102448569B/zh not_active Expired - Fee Related
- 2010-05-26 EP EP10722007.1A patent/EP2435151B1/de not_active Not-in-force
- 2010-05-26 SG SG2011080348A patent/SG175850A1/en unknown
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Publication number | Publication date |
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SG175850A1 (en) | 2011-12-29 |
KR101743310B1 (ko) | 2017-06-15 |
EP2435151B1 (de) | 2016-05-25 |
KR20120036814A (ko) | 2012-04-18 |
US8497345B2 (en) | 2013-07-30 |
US20120123084A1 (en) | 2012-05-17 |
CN102448569B (zh) | 2016-06-01 |
WO2010139413A1 (de) | 2010-12-09 |
EP2255860A1 (de) | 2010-12-01 |
JP2012528896A (ja) | 2012-11-15 |
EP2435151A1 (de) | 2012-04-04 |
CN102448569A (zh) | 2012-05-09 |
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