TW546315B - Transparent, non-elastomeric, high hardness, impact resistant polyurethane material and eyewear lens made therefrom - Google Patents
Transparent, non-elastomeric, high hardness, impact resistant polyurethane material and eyewear lens made therefrom Download PDFInfo
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- TW546315B TW546315B TW087119961A TW87119961A TW546315B TW 546315 B TW546315 B TW 546315B TW 087119961 A TW087119961 A TW 087119961A TW 87119961 A TW87119961 A TW 87119961A TW 546315 B TW546315 B TW 546315B
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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Description
546315
本發明為美國專利申請 案,該案又為美國專利申 案,二案皆併述於此以供 背景 ~ 案第0 8 /59 5,262號之部份 請案第08/^82, 5 62號之部 參考。 連續 份連續 發明領域 光學透明耐熱及耐衝擊性聚气 本發明係關於一種剛性 基甲酸乙酯。 發明背景 目前 ’全部光學透明塑膠材料比較其耐衝擊性 料為聚碳酸酯。此種材料夕姓%炎y H ^ 之b準材 變之溫度及壓力。聚碳酸酯之埶畸抖進订對 力為約280度F。 du皿度於264PS1纖維應 厚度0· 25吋之聚碳酸酯擠塑薄片具有〇· 22卡規FSp(斷片 模擬投射彈)V-50耐衝擊等級為925f t· /sec。ν-5〇為5〇%22 卡規投射彈經由0 · 2 5吋聚碳酸酯薄片發射貫穿置於聚碳酸 薄片背面後方6吋的22毫米厚度20 24 T6鋁片(”見證片”) 的速度測量值。 美國專利3,8 6 6,2 4 2 (併述於此以供參考)揭示一種聚氨 基甲酸乙酯聚合物保護屏。聚氨基甲酸乙酯之生產方法係 經由: (a) 分子量約700至1,〇〇〇之聚乙二醇或聚酯二醇與亞甲 基-貳(異氰酸環己酯)以約3 NCO對每個羥基之當量比反應。 形成預聚物,及 (b) 預聚物與芳族胺固化劑以〇 · 9 〇對1. 〇4NH9/ 1. 0NCO之
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當里比反應,該芳族胺固化劑介於二芳族環間有一個亞甲 基橋,如4, 4’ -亞曱基貳(2 -氯苯胺)。 美國專利4, 80 8, 690 (併述於此以供參考)揭示一種由多 兀醇固化預聚物製備之透明聚氨基曱酸乙酯聚合物。預聚 物係由聚異氰酸酯及至少一種多官能含羥基中間物製備。 美國專利4, 20 8, 5 0 7揭示一種撓性聚氨基曱酸乙酯—脲彈 ,體,其製法係經由反應:(A) 一種預聚物,其係經由分子· 量6 0 0至1〇, 〇〇〇之大致雙官能多羥化合物與含有至少一nc〇 , 基鍵結至環月曰知結構的有機二異氰酸酯,以可提供她· NCO比為1:1·2至1:10之數量反應獲得,與(B)3,3/,、5y5,: 四甲基4,4 - 一胺基二苯基曱院’ A及B係以約ι:〇·8至 1 : 1 · 2之莫耳比反應。 · · 發明概沭 本發明之光學澄清聚氨基甲酸乙酯之製法可經由首先生 產預聚物,其係經由一或多種聚酯二醇類,聚己内酯二醇 類’聚ϋ二醇類或聚碳酸酯二醇類具有重均分子量約4〇〇 至約2 0 0 〇與脂族或環脂族二異氰酸酯以對每個⑽約2 · $至 4· 0 NCO之當量比反應生產。然後預聚物與芳族二胺固化 劑如二乙基甲苯二胺,以約〇· 85至1· 02ΝΗ2/1· 〇NCO,較佳❿ 約 〇·90 至 l.〇NH2/l.〇NCO,及更佳約 0.92 至 〇.96NH2/l.〇NC土〇 之當量比反應。 本發明之聚氨基甲酸乙酯特別可用於需要絕佳耐衝擊性 加上高熱畸變溫度之透明用途,例如建築玻璃帷幕牆,汽 車鑲後玻璃,警用盾牌,飛機座艙罩,面罩,帽舌,光與
546315 案號 87119961 五、發明說明(3) 曰 修正 鏡片及太陽鏡片,護目鏡及透明i曱。 ^發明之目的係提供比較先前技術材料具有絕佳光學透 明聚氨基甲酸乙醋類。抗性及南熱崎變溫度之透 耐用於商業用途成本降低之透明 目的係藉由縮短 度及縮短模具停駐時間辦 ^ J降低I私溫 之製造過程。 1 9進透明耐衝擊性聚氨基甲酸乙酯 此等及其它本發明之目的 ”附之申請專利範心月:細節說明、實例 細說明 一進步細即。 本發明之聚氨基甲酸乙,從丄 、 類,含羥基中間物,及二二脂族或環脂族二異氰酸酯 成份之細節說明。 、—私:固化劑製備。後文為各該 金間物 可用於製備本發明之聚_ 包括聚龜二醇類1已内;基!酸乙醋類之含經基中間物 酯二醇類,其具有重均八:=醇類,聚醚二醇類及聚碳酸 約4〇〇至約1〇00。 刀于量由約400至約200 0,及較佳 有用的聚酯二醇類包括一 羧酸(如己二酸,丁二酸及八或夕種含4至10個碳原子之二 碳原子之低分子量二醇類(:一酸)與一或多種含2至10個 醇,1,4- 丁二醇,新戊:(如=醇,丙二醇,二乙二 - x 一知,1,6-己二醇及1,10 -癸二醇) 87119961.ptc 第7頁 修正頁 2_·〇1·21·〇〇7 546315
之酯化產物。較佳聚酯二醇類為己二酸與含2至1〇個碳原 子之二醇類之酯化產物。 有用的聚己内,二醇類包括ε—己内醋與一或多種上列 低分子量二醇類之反應產物。此外,冑用的含羥基中間物 包括由或夕種低分子量二羧酸,如己二酸及己内酯類與 -或多種上列低分子量二醇類生產的過醋類。 較佳聚S旨二醇及聚己内g旨二醇可藉幕所周知之_化或轉 移酯化程序衍生而得,例如述於參考文獻D M. y〇ung,F· Hostettler et al., "Polyesters from Lactone'1,
Union Carbide F-40 , p·147 。 有用的一醇類包括聚四亞甲基醚二醇。 有用的聚碳酸酯二醇類包括脂族聚碳酸酯二醇類。較佳 脂族聚碳酸酯二醇類係由Enichem以商品*Ravecarb 102(分子量=1,〇〇〇)及Ravecarb 106(分子量=2,〇〇〇)製造 出售。 最佳含說基中間物為:(a)己二酸與一或多種選自1,4一丁 二醇,1,6-己二醇,新戊二醇及ι,ι〇_癸二醇之酯化產 物;(b)e -己内酯與一或多種選自1,4 - 丁二醇,1,6-己二 醇,新戊二醇及1,1()-癸二醇之二醇之反應產物;(c)聚四 亞甲基二醇;(d)脂族聚碳酸酯二醇類,及(e)此等含羥基 中間物之混合物。 5異氰酸酯類 可用於製備本發明之聚氨基甲酸乙酯類之脂族或環脂族 二異氰酸酯類包括二環己基甲烷二異氰酸酯,及較佳其異
第8頁 修正買2〇〇0· 01.21. 〇〇8 546315 ----案號87119961 _年月 日 修正 五、發明說明(5) 一 " '〜 構物混合物含有約2 〇 -1 〇 〇 % 4,4,_亞甲基貳(環己基異氰酸 酉旨)之反,反-異構物,後文稱做” PICMH (對異氰酸根環已基 甲烧)。其它本發明有用的通常存在於二環己基曱烷二異 氮酸醋之位置及/或立體異構物混合物之成份為p丨CM之 順’反及順’順-異構物及2, 4,-亞甲基貳(環己基異氰酸 酯)之立體異構物。此等及反,反PICM異構物之存在量可 藉由用於製備二環己基甲烷二異氰酸酯之程序控制。較佳 二異氰酸酿類為異構物p ICM混合物。特佳混合物含有不低 於約20%反,反-異構物及不多於約2〇%4, 4,—亞甲基貳(環 己基異氰酸酯)之順,順—異構物。三種44,—亞甲基貳(環 己基異乱酸S曰)之異構物顯示如後·· 反,反
NCO
^^TNCO 順,反
NCO
NCO 〇 順,順 本發明使用的PICM可藉業界眾所周知之程序以光氣處理 對應4, 4’ -亞甲基貳(環己基胺)(PACM)製備,例如揭示於 美國專利 2, 644, 007,2, 680, 127 及2, 908, 703,併述於此 以供參考。PACM異構物當進行光氣處理反應時,於室溫獲
87119961.ptc 第9頁 修正頁 2000. 〇!. 21. 009 546315 修正 妒由,ί 。卩彳刀液相或固相之1"1CM。P ACM異構物混合物可 下八二#亞曱基一胺基或經由於水及醇如曱醇及乙醇存在 2 ^又…晶PACM異構物混合物獲得。 與二^有用的知私及環脂族二異氰酸酯類包括得自A r c 〇化 二二3一異氰酸根—甲基―3, 5, 5—三甲基環己基異氰酸6旨 (IpDI”),具如下結構式:叫
公司所’間—四甲基二甲苯二異氰酸酯(1,3-貳U- 二,:土一1一甲基乙基)一苯),其商標名為TMXDI ®(間)脂 矢”氰酸酯,及具如下結構式: 巧 。心4^^ 一; 太 Uz 缺t 1明書及申請專利範圍内所參照脂族及環脂族二異氰 2知:、、、欲包含式R—(NC〇、之化合物,R為脂族基、環脂族 土、或為以烷基取代之芳族,其中氮鍵結至烷基取代基, 但不包含此式之下R為芳族基而氮鍵結至芳環上。 -一胺固化齊丨
較佳用於製備本發明之聚氨基甲酸乙酯之芳族二胺固化 劑為2, 4j二胺基一3, 5 -二乙基—甲苯,2, 6一二胺基一3, 5一二 乙基曱苯及其混合物(合稱π二乙基甲苯二胺,,或,,DETDAf,) ,其係由Albemarle公司以商品名Ethacure 100出售。 DETDA於室溫為液體具有黏度於25°C為156cs。DETDA為異 構物’ 2, 4-異構物占75-81%而2, 6-異構物占18-24%。 DETDA具如下結構式:
87119961.ptc 第10頁 修正頁 2000.01.21.010 546315 案號87119961 年月日 修正
87119961.ptc 第21頁 修正頁 2000.01.21.021
Claims (1)
- 5_15各泰 1 89· i.f2i , : ^k號87119961_年月曰 修正_絛正太 _ ----------------—y 卜 <*»-·!*« *»«Α-ΛίΜ«·Λί*» 六、申請專利範圍 1. 一種透明、非彈性、高硬度之耐衝擊性聚氨基甲酸乙 酯材料,其包含下列之反應產物: (a) 聚氨基甲酸乙酯預聚物,其係經由脂族或環脂族二 異氰酸酯與至少一種重均分子量4 0 0至2 0 0 0之選自包括聚 酯二醇類,聚己内酯二醇類,聚醚二醇類及聚酸酯二醇 類;其混合物之含羥基中間物以2.5至4.0NCO/1.0 0H當量 比反應製備;及 (b) 至少一種第一芳族二胺固化劑選自包括2, 4_二胺基 , -3,5 -二乙基甲苯,2, 6 -二胺基-3, 5 -二乙基甲苯及其混合 物以0. 85至1. 02ΝΗ2/1· 0 NCO當量比反應。 2. 如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該聚氨基曱酸乙酯材料為聚氨基曱酸乙酯預聚物,至少一 種第一芳族二胺固化劑,及至少一種第二二胺固化劑選自 包括下式化合物所得反應產物: Ri Ri I I H2N ^ . nh2% 其中匕及匕各自分別選自包括甲基,乙基,丙基及異丙基 及匕係選自包括氫及氯。 3.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該二異氰酸酯係選自包括4, 4’ -亞曱基貳(環己基異氰酸 酯),3-異氰酸根-曱基-3, 5, 5-三曱基環己基異氰酸酯, 間-四曱基二曱苯二異氰酸酯及其混合物。87119961.ptc 第22頁 2000.01.21.022 546315 修正 案鍊 8711QQR1 六、申請專利範圍 二ί m利1a圍第1項之聚氨基甲酸乙酯材料,其中 ΐ:二1 L旨材料具有熱畸變溫度於264Psi係於210 度F至3 2 5度F之範圍。 二ΐ Hi利範圍第1項之聚氨基甲酸乙醋材料,其中 度F ^欠乙醋材枓具有熱畸變溫度於264pS 1至少為 二:i : ί利犯圍第1項之聚氨基甲酸乙酯材料,其中 基甲酸乙醋材料具有熱崎變溫度於264psi至少為 範圍第1項之聚氨基甲酸乙醋材料,其中 基曱酸乙醋材料為光學透明具有發光透射率至少 8:=請專利範圍第i項之聚氨基甲酸乙醋材料 咸1乱基曱酸乙醋材料之0.25吋厚度薄片具有^5〇 〇、中 卡規FSP評分至少11〇〇呎/秒。 · 9二如申清專利範圍第1項之聚氨基甲酸乙酯材料,其中 τ間物之重均分子量為40 0至1 000。 > 1^·、〜如申請專利範圍第1項之聚氨基甲酸乙酯材料,复 瀘』3羥基中間物係選自包括:(a)己二酸與一種或多種選白 包括1,4 肛、目 一 一醇,I 6-己二醇,新戊二醇及1,10 —癸二醇 之一醇類之酯化產物;(b) ε -己内酯與一種或多種選自包546315 _案號87119961_年月曰 修正_ 六、申請專利範圍 括1,4- 丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之 二醇類之反應產物;(c)聚四亞曱基二醇;(d)脂族聚碳酸 酯二醇類;及(e)此種含羥基中間物之混合物。 1 2.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該環脂族二異氰酸酯為4, 4’ -亞曱基貳(環己基異氰酸酯) 之異構物混合物其包含至少20% 4, 4’ -亞曱基貳(環己基異 氰酸酯)之反,反-異構物。 1 3.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 , 該預聚物進一步包含一種紫外光安定劑。 . 1 4.如申請專利範圍第1 3項之聚氨基甲酸乙酯材料,其 f 中該紫外光安定劑係選自包括苯并三唑類,封阻胺光安定 劑,及其混合物。 1 5.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該預聚物進一步包含一種抗氧化劑。 1 6.如申請專利範圍第1 6項之聚氨基甲酸乙酯材料,其 中該抗氧化劑為多官能封阻酚。 1 7.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該聚氨基曱酸乙酯材料當使用異丙醇測量時具有應力耐裂 性大於70 0 0磅/平方吋。 1 8.如申請專利範圍第1項之聚氨基曱酸乙酯材料,其中 該預聚物進一步包含一種三元醇其含量足夠產生1 %交聯, 以反應物之當量為基準。 1 9.如申請專利範圍第1 8項之聚氨基甲酸乙酯材料,其 中該三元醇係選自包括三羥甲基乙烷,三羥曱基丙烷及其87119961.ptc 第24頁 2000.01.21.024 546315 案號 87119%1__年月日_ί±£-_—_ — 六、申請專利範圍 混合物。 2 0 · —種透明、非彈性、高硬度之耐衝擊性聚氨基曱酸 乙酯之材料,其包含下述反應產物:(a) —種聚氨基曱酸乙酯預聚物,其係經由一種選自包 括4, 4’ -亞曱基貳(環己基異氰酸酯),3-異氰酸根甲基-3, 5, 5-三曱基環己基異氰酸酯,間-四甲基二甲苯二異氰酸 酯及其混合物之二異氰酸酯與至少一種具有重均分子量 400至2000之選自包括:(a)己二酸與一種或多種選自包括 1,4-丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之 二醇類之酯化產物;(b)e -己内酯與一種或多種選自包括 1,4- 丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之二 醇類之反應產物;(c )聚四亞甲基二醇;(d )脂族聚碳酸酯 二醇類’及(e)此種含羥基中間物之混合物以2. 5至4. 0 NCO/1· 0 OH之當量比反應製備; (b) 至少一種二胺固化劑其係選自包括2, 4一二胺基—3, 5-二乙基曱苯,2, 6 -二胺基-3, 5 -二乙基甲苯及其混合物, 以0·95至1·〇2ΝΗ2/1·0 NCO之當量比反應,其中該聚氨基 曱酸乙S旨材料具有熱畸變溫度於Μ 4psi至少為30 0度F。2 1 · —種眼鏡鏡片,其係由申請專利範圍第1項之聚氨基 甲酸乙酯材料製得。 2 2 ·如申請專利範圍第21項之眼鏡鏡片,其中該鏡片係 選自由太陽眼鏡鏡片、眼科鏡片及保護鏡片所組成之群。 23. —種眼鏡鏡片,其係由申請專利範圍第2〇項之聚 基甲酸乙酯材料製得。第 25 頁 200〇·〇ι·2ΐ·025 546315曰 修正 、登白士如申θ請專利範圍第23項之眼鏡鏡片,其中該鏡片係 5 ^太h陽眼鏡鏡片、眼科鏡片及保護鏡片所組成之群。 該- ·胺°申請專利範圍第1項之聚氨基甲酸乙酯材料,1中 2;如化:為經色彩穩定化。 中該-申请專利範圍第20項之聚氨基甲酸乙酯材料,发 ^劑為經色彩穩定化。 ^ 中聚与*申凊專利範圍第20項之聚氨基甲酸乙酯材料,盆 80%。 〇 ®曰材枓為光學透明且具有發光透射率至少 2 8 女 中聚_ 1申清專利範圍第20項之聚氨基曱酸乙醋材料’其 規FSp"練\甲酸乙酿材料之〇· 25吋厚度薄片具有卜5 0 0· 22卡 2 9 °为至少11 0 0呎/每秒。 中該2、,申明專利範圍第2 0項之聚氨基曱酸乙酯材料,其 30.H基/間物之重均分子量為400至1〇〇〇 ° 中該二s /月專利範圍第2 〇項之聚氨基甲酸乙s旨材料’其 構物ί二2 ΐs旨為4,4’ -亞曱基戴(環己基異氰酸_)之異 酉旨)物其包含至少20% 4,4,_亞甲基武(環己基異氰酸 31反,反-異構物。 中該預臂申:、隹專利乾圍第20項之聚氨基甲酸乙酯材料,其 β歎物進一步句冬_ 32·如申杜直w匕3種紫外光安定劑。 3曱δ月專利範圚篦q 1 申明專利la圍第20項之聚氨基甲酸乙酯材料,其87ll"6l.ptc t中該紫外光安定劑俾/自V?聚氨基甲酸乙_ ’ ^ 〜及其混合物。 匕括苯开三唑類,封阻胺光安定 第26頁 2000.01.21.026 546315 •… _案號87119961_年月曰 修正_ 六、申請專利範圍 中該預聚物進一步包含一種抗氧化劑。 3 4.如申請專利範圍第33項之聚氨基曱酸乙酯材料,其 中該抗氧化劑為多官能封阻酚。 3 5.如申請專利範圍第2 0項之聚氨基曱酸乙酯材料,其 中該聚氨基甲酸乙酯材料當使用異丙醇測量時具有應力耐 裂性大於70 0 0磅/平方吋。 3 6.如申請專利範圍第20項之聚氨基甲酸乙酯材料,其 中該預聚物進一步包含一種三元醇其含量足夠產生1%交 、 聯,以反應物之當量為基準。 . 37.如申請專利範圍第36項之聚氨基甲酸乙酯材料,其 4 中該三元醇係選自包括三羥甲基乙烷,三羥甲基丙烷及其 混合物。87119961.ptc 第27頁 2000.01.21.027
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- 1998-10-07 CN CN2004101006196A patent/CN1654499B/zh not_active Expired - Fee Related
- 1998-10-07 ES ES98948609T patent/ES2227879T3/es not_active Expired - Lifetime
- 1998-10-07 DE DE69825796T patent/DE69825796T2/de not_active Expired - Lifetime
- 1998-10-07 EP EP98948609A patent/EP1137684B1/en not_active Expired - Lifetime
- 1998-10-07 AU AU95144/98A patent/AU762846B2/en not_active Ceased
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- 1998-10-07 KR KR10-2001-7002669A patent/KR100526050B1/ko not_active IP Right Cessation
- 1998-10-07 WO PCT/US1998/021250 patent/WO2000014137A1/en active IP Right Grant
- 1998-10-07 CN CNB988142996A patent/CN1188442C/zh not_active Expired - Fee Related
- 1998-10-07 CA CA002342851A patent/CA2342851C/en not_active Expired - Lifetime
- 1998-10-07 AT AT98948609T patent/ATE274004T1/de active
- 1998-10-26 MY MYPI98004863A patent/MY118596A/en unknown
- 1998-12-02 TW TW087119961A patent/TW546315B/zh not_active IP Right Cessation
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2001
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- 2001-03-01 NO NO20011064A patent/NO328118B1/no not_active IP Right Cessation
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CN1654499A (zh) | 2005-08-17 |
KR100526050B1 (ko) | 2005-11-08 |
WO2000014137A1 (en) | 2000-03-16 |
IL141709A0 (en) | 2002-03-10 |
AU9514498A (en) | 2000-03-27 |
CN1188442C (zh) | 2005-02-09 |
EP1137684A1 (en) | 2001-10-04 |
CA2342851A1 (en) | 2000-03-16 |
HK1042311A1 (en) | 2002-08-09 |
ES2227879T3 (es) | 2005-04-01 |
JP4898001B2 (ja) | 2012-03-14 |
CA2342851C (en) | 2009-12-15 |
MXPA01002291A (es) | 2002-05-08 |
CN1654499B (zh) | 2012-05-30 |
JP2002524591A (ja) | 2002-08-06 |
KR20010074892A (ko) | 2001-08-09 |
ID29092A (id) | 2001-07-26 |
EP1137684B1 (en) | 2004-08-18 |
ATE274004T1 (de) | 2004-09-15 |
CN1314922A (zh) | 2001-09-26 |
DE69825796T2 (de) | 2005-01-27 |
DE69825796D1 (de) | 2004-09-23 |
EP1137684A4 (en) | 2002-03-20 |
NO20011064L (no) | 2001-04-23 |
MY118596A (en) | 2004-12-31 |
HK1042311B (zh) | 2005-02-04 |
US6127505A (en) | 2000-10-03 |
NO328118B1 (no) | 2009-12-14 |
IL141709A (en) | 2010-05-17 |
AU762846B2 (en) | 2003-07-10 |
NO20011064D0 (no) | 2001-03-01 |
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