JP5364587B2 - 改良された低温靱性および外観を有する熱可塑性成形組成物 - Google Patents
改良された低温靱性および外観を有する熱可塑性成形組成物 Download PDFInfo
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- JP5364587B2 JP5364587B2 JP2009539300A JP2009539300A JP5364587B2 JP 5364587 B2 JP5364587 B2 JP 5364587B2 JP 2009539300 A JP2009539300 A JP 2009539300A JP 2009539300 A JP2009539300 A JP 2009539300A JP 5364587 B2 JP5364587 B2 JP 5364587B2
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- 238000011109 contamination Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- AKIDPNOWIHDLBQ-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarbonyl chloride Chemical compound C1=CC(C(Cl)=O)=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1C(Cl)=O AKIDPNOWIHDLBQ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
ポリカーボネート、ポリアルキレンテレフタレートおよびエラストマー耐衝撃性改良剤を含む熱可塑性成形組成物を開示する。この耐衝撃性改良剤は、pH7以下かつナトリウムイオン含量500ppm以下であり、コア/シェルモルホロジーで特徴付けられ、コアは重合ブタジエン構造ユニットを含み、シェルは重合メタクリレート構造ユニットを含む。スチレン構造ユニットがコア中に存在する場合、シェル中のメタクリレート対コア中のスチレンの重量比は1.5以上である。コアは、耐衝撃性改良剤の重量に対して40〜70パーセントの量で存在し、シェルのガラス転移温度は23℃以上である。この組成物は、その改良された表面品質および低温靱性で特徴付けられる。
本発明の熱可塑性成形組成物は、ポリカーボネート25〜95重量部(pbw)、好ましくは40〜80pbw、ポリアルキレンテレフタレート5〜75pbw、好ましくは20〜60pbw、および耐衝撃性改良剤、ポリカーボネートとポリアルキレンテレフタレートとの総重量に対して1〜40パーセント、好ましくは5〜20パーセントを含む。この組成物は、その低温衝撃強さおよび良好な外観で特徴付けられる。
本明細書中で使用される用語「芳香族ポリカーボネート」は、一般的に、ホモポリカーボネートおよびコポリカーボネートをいい、ポリエステルカーボネートを含む。これらの材料はよく知られており、市販されている。
A は、単結合、C1−〜C5−アルキレン、C2−〜C5−アルキリデン、C5−〜C6−シクロアルキリデン、−O−、−SO−、−CO−、−S−、−SO2−、任意にヘテロ原子を含んでいてもよい別の芳香環が縮合していてもよいC6−〜C12−アリーレン、または式(II)もしくは(III)
B は、互いに独立して、C1−〜C12−アルキル、好ましくはメチルであり、
x は、互いに独立して、0、1または2であり、
p は、1または0であり、かつ
R5およびR6 は、それぞれのX1に対して個々に選択され、それぞれ互いに独立して、水素またはC1〜C6−アルキル、好ましくは水素、メチルまたはエチルであり、
X1 は、炭素であり、かつ
m は、4〜7の整数、好ましくは4または5である。但し、少なくとも一つの原子X1において、R5とR6は両方ともアルキル基である。)
の化合物である。
本発明との関連で好適なポリアルキレンテレフタレートとしては、ホモポリマーおよびコポリマー樹脂であって、その分子構造がカルボン酸から誘導される少なくとも一つの結合を含み、好ましくは炭酸から誘導される結合を含まないホモポリマーおよびコポリマー樹脂が挙げられる。これらは既知の樹脂であり、ジオール成分と二酸との既知の方法による縮合またはエステル交換重合によって製造されうる。例えば、シクロヘキサンジメタノールとエチレングリコールとテレフタル酸またはテレフタル酸とイソフタル酸との組み合わせとの縮合によって誘導されるエステルである。シクロヘキサンジメタノールとエチレングリコールと1,4−シクロヘキサンジカルボン酸との縮合から誘導されるポリエステルもまた好適である。好適な樹脂としては、ポリ(アルキレンジカルボキシレート)、特にポリ(エチレンテレフタレート)(PET)、ポリ(1,4−ブチレンテレフタレート)(PBT)、ポリ(トリメチレンテレフタレート)(PTT)、ポリ(エチレンナフタレート)(PEN)、ポリ(ブチレンナフタレート)(PBN)、ポリ(シクロヘキサンジメタノールテレフタレート)(PCT)、ポリ(シクロヘキサンジメタノール−co−エチレンテレフタレート)(PETGまたはPCTG)、およびポリ(1,4−シクロヘキサンジメチル−1,4−シクロヘキサンジカルボキシレート)(PCCD)が挙げられる。
成分(C)は、コア/シェルモルホロジーを有する耐衝撃性改良剤であり、架橋エラストマーコアが(共)重合ブタジエンを含み、グラフトシェルであってガラス転移温度が23℃以上、好ましくは80℃以上、最も好ましくは90℃以上であるグラフトシェルが(コ)ポリメタクリレートを含み、ゴム含量が耐衝撃性改良剤の重量に対して約40〜70重量パーセント、好ましくは50〜70重量パーセント、最も好ましくは60〜70重量パーセントであり、ナトリウムイオン含量が500ppm以下、好ましくは1〜400ppm、より好ましくは2〜100ppmであり、かつ、pHが7以下、好ましくは4〜7であることを特徴とする。エラストマーコアは、一種類以上のビニルモノマー、好ましくは炭素原子を3〜12個有するビニルモノマー、例えばスチレンおよびメチルスチレン、と共重合したブタジエンを含みうる(但し、コアが共重合スチレンを含む態様では、シェル中のメタクリレート対スチレンの重量比は1.5以上である。)。組成的に、シェルは、任意に少なくとも一種類のビニルコモノマー、好ましくはスチレンと共重合してもよい重合メタクリレート、好ましくはメチルメタクリレート、を含む。
本発明による組成物を、製造し、その特性を決定した。以下に記述される組成物の製造において、成分は、以下のものである。
ポリカーボネート1: ASTM D−1238(300℃、1200g負荷)による溶融流量が約6.5グラム/10分であることを特徴とするビスフェノールAベースのホモポリカーボネート(Makrolon 3108ポリカーボネート)
ポリカーボネート2: ASTM D−1238(300℃、1200g負荷)による溶融流量が約13グラム/10分であることを特徴とするビスフェノールAベースのホモポリカーボネート(Makrolon 2608ポリカーボネート)
PET1: 固有粘度が0.94であることを特徴とするポリエチレンテレフタレート
PET2: 固有粘度が0.6であることを特徴とするポリエチレンテレフタレート
耐衝撃性改良剤: 以下の表は、例示される組成物中に含まれる耐衝撃性改良剤の組成を記述している。これらの耐衝撃性改良剤は、コア/シェル構造であって、ポリメチルメタクリレートおよび、任意にスチレンをシェルに含み、ポリブタジエンまたはコポリブタジエンをコアに含むコア/シェル構造を有する。耐衝撃性改良剤3は、本発明の耐衝撃性改良剤であり、別の耐衝撃性改良剤は、全て比較の耐衝撃性改良剤である。
別の組成物を、以下に示されるように製造し、評価した。
ポリカーボネート3: ASTM D−1238(300℃、1200g負荷)による溶融流量が約20グラム/10分であることを特徴とするビスフェノールAベースのホモポリカーボネート(Makrolon 2405ポリカーボネート)
別の組成物を以下に示されるように製造し、評価した。
ポリカーボネート4: ASTM D−1238(300℃、1200g負荷)による溶融流量が約10グラム/10分であることを特徴とするビスフェノールAベースのホモポリカーボネート(Makrolon 2808ポリカーボネート)
PBT: 商標Pocan B1300のもとで入手可能なLanxess社製のポリブチレンテレフタレート(PBT)
PMX: 等量(38.2%)の粉末PBTとポリカーボネート、KU3−2213 9.1%、Black Pearls 800 9.2%、Irgafos 168 3.0%を含むプレミックス。KU3−2213はエステル交換クエンチャー(quencher)であり、Black Pearls 800はカーボンブラックであり、Irgafos 168は熱安定剤である。PMXは本発明との関連で臨界を有さない。
Claims (11)
- (a)ポリカーボネート、
(b)ポリアルキレンテレフタレートおよび
(c)pH7以下であり、二峰性粒度分布のピークが50nmと550nmにあり、かつナトリウムイオン含量1〜500ppmの耐衝撃性改良剤であって、コア/シェルモルホロジーで特徴付けられ、コアが重合ブタジエン構造ユニットを含み、シェルが重合メタクリレート構造ユニットを含み、前記コアが該耐衝撃性改良剤の重量に対して40〜70パーセントの量で存在し、前記シェルが23℃以上のガラス転移温度を有する耐衝撃性改良剤であって、コアが共重合スチレンを含み、シェル中のメタクリレート対コア中の該スチレンの重量比1.5未満である耐衝撃性改良剤を含まない耐衝撃性改良剤
を含有する熱可塑性成形組成物。 - 該ポリカーボネートが25〜95(pbw)の量で存在し、該ポリアルキレンテレフタレートが5〜75pbwの量で存在し、該耐衝撃性改良剤がポリカーボネートとポリアルキレンテレフタレートとの総重量に対して1〜40パーセントの量で存在する、請求項1に記載の組成物。
- 該ポリカーボネートが40〜80pbwの量で存在し、該ポリアルキレンテレフタレートが20〜60pbwの量で存在し、かつ該耐衝撃性改良剤がポリカーボネートとポリアルキレンテレフタレートとの総重量に対して5〜20パーセントの量で存在する、請求項1に記載の組成物。
- 該ポリアルキレンテレフタレートがポリエチレンテレフタレートである、請求項1に記載の組成物。
- 該ポリアルキレンテレフタレートがポリブチレンテレフタレートである、請求項1に記載の組成物。
- 該耐衝撃性改良剤の体積平均粒度が10nm〜2ミクロンである、請求項1に記載の組成物。
- 前記シェルのガラス転移温度が80℃以上である、請求項1に記載の組成物。
- コアが耐衝撃性改良剤の重量に対して50〜70重量パーセントの量で存在する、請求項1に記載の組成物。
- 前記ナトリウムイオン含量が1〜400ppmである、請求項1に記載の組成物。
- 前記コアが少なくとも一種類のビニルモノマーと共重合したブタジエンを含む、請求項1に記載の組成物。
- ビニルモノマーがスチレンである、請求項10に記載の組成物。
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US11/607,682 US7524898B2 (en) | 2006-12-01 | 2006-12-01 | Thermoplastic molding composition having improved toughness at low temperatures and surface appearance |
US11/607,682 | 2006-12-01 | ||
PCT/US2007/024478 WO2008069935A1 (en) | 2006-12-01 | 2007-11-28 | Thermoplastic molding composition having improved toughness at low temperatures and surface appearance |
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JP5364587B2 true JP5364587B2 (ja) | 2013-12-11 |
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US (1) | US7524898B2 (ja) |
EP (1) | EP2099864B1 (ja) |
JP (1) | JP5364587B2 (ja) |
KR (1) | KR101517250B1 (ja) |
CN (1) | CN101547973B (ja) |
BR (1) | BRPI0719382A2 (ja) |
CA (1) | CA2670729C (ja) |
ES (1) | ES2639419T3 (ja) |
MX (1) | MX2009005669A (ja) |
RU (1) | RU2009124742A (ja) |
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WO (1) | WO2008069935A1 (ja) |
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TR201900151T4 (tr) * | 2008-08-29 | 2019-02-21 | Arkema Inc | İşlevselleştirilmiş iki modelli darbe modifiye ediciler. |
EP2210916A1 (en) * | 2009-01-23 | 2010-07-28 | Bayer MaterialScience AG | Polycarbonate molding composition |
DE102009017724A1 (de) | 2009-04-11 | 2010-10-14 | Clariant International Limited | Bleichmittelgranulate |
DE102009017722A1 (de) | 2009-04-11 | 2010-10-14 | Clariant International Limited | Bleichmittelgranulate mit Aktivcoating |
JP5761722B2 (ja) * | 2009-09-24 | 2015-08-12 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトBayer MaterialScience AG | 改良された燃焼挙動を有する射出成形多部材複合系 |
CN102382438A (zh) * | 2010-09-01 | 2012-03-21 | E.I.内穆尔杜邦公司 | 具有改进的熔体流动性的热塑性组合物 |
FR2969158B1 (fr) * | 2010-12-15 | 2013-01-18 | Arkema France | Procede pour modifiants chocs et composition thermoplastique modifiee choc ayant une resistance hydrolytique amelioree |
FR2969167B1 (fr) * | 2010-12-15 | 2013-01-11 | Arkema France | Composition thermoplastique modifiee choc amelioree |
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US8440762B2 (en) * | 2011-01-14 | 2013-05-14 | Sabic Innovative Plastics Ip B.V. | Polymer compositions, method of manufacture, and articles formed therefrom |
CN102888086A (zh) * | 2011-07-22 | 2013-01-23 | 纳幕尔杜邦公司 | 具有改进的溶体流动性的阻燃性组合物 |
US9332802B2 (en) * | 2011-12-30 | 2016-05-10 | Ticona Llc | Molded polymer articles for use in low temperatures having a low rigidity factor |
DE102013010549A1 (de) | 2013-06-15 | 2014-12-18 | Clariant International Ltd. | Bleichmittel-Co-Granulate |
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US10240036B2 (en) | 2015-04-30 | 2019-03-26 | Samsung Electronics Co., Ltd. | Polymer composition, molded article, and method of manufacturing the molded article |
KR102360702B1 (ko) * | 2016-06-27 | 2022-02-10 | 코베스트로 도이칠란트 아게 | 폴리카르보네이트 조성물 및 그를 포함하는 물품 |
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JPH02225510A (ja) * | 1988-11-09 | 1990-09-07 | Takeda Chem Ind Ltd | 相互貫通高分子対を形成するポリマー粒子 |
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US5082897A (en) * | 1989-12-15 | 1992-01-21 | Monsanto Company | Polymer blends of polycarbonate, pctg and abs |
US5674928A (en) * | 1995-09-21 | 1997-10-07 | General Electric Company | Thermoplastic resin compositions containing a high hydroxyl polyester and a polycarbonate, and articles made therefrom |
DE69715695T2 (de) | 1996-02-02 | 2004-02-26 | General Electric Co. | Schlagzähe Polycarbonat-/ Polyestermischungen mit hoher Wetterbeständigkeit |
US6545089B1 (en) * | 1997-09-04 | 2003-04-08 | General Electric Company | Impact modified carbonnate polymer composition having improved resistance to degradation and improved thermal stability |
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US6989190B2 (en) * | 2000-10-17 | 2006-01-24 | General Electric Company | Transparent polycarbonate polyester composition and process |
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EP2099864A1 (en) | 2009-09-16 |
TWI419927B (zh) | 2013-12-21 |
CA2670729C (en) | 2015-05-05 |
KR101517250B1 (ko) | 2015-05-07 |
MX2009005669A (es) | 2009-06-08 |
BRPI0719382A2 (pt) | 2014-02-18 |
JP2010511741A (ja) | 2010-04-15 |
KR20090083913A (ko) | 2009-08-04 |
CN101547973B (zh) | 2012-01-11 |
EP2099864B1 (en) | 2017-06-07 |
US7524898B2 (en) | 2009-04-28 |
WO2008069935A1 (en) | 2008-06-12 |
US20080132641A1 (en) | 2008-06-05 |
ES2639419T3 (es) | 2017-10-26 |
CA2670729A1 (en) | 2008-06-12 |
TW200844178A (en) | 2008-11-16 |
RU2009124742A (ru) | 2011-01-10 |
CN101547973A (zh) | 2009-09-30 |
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