CN1151186C - 可折叠的眼科及耳鼻喉科器件材料 - Google Patents
可折叠的眼科及耳鼻喉科器件材料Info
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
Abstract
公开了软质、高折射率的聚丙烯酸类材料,此材料的伸长率至少为150%。这些材料,特别用于眼内透镜材料,含有芳基丙烯酸类疏水单体作为单一的主要器件形成单体。除了用作眼内透镜材料外,本发明的材料也适用于其它眼科或耳鼻喉科器件,例如接触镜片、人工角膜、角膜嵌体或环、耳科通气管以及鼻植入物。
Description
发明领域
本发明涉及聚丙烯酸类器件材料。具体地说,本发明涉及软质、高折射率的聚丙烯酸类器件材料,特别适用于眼内透镜(IOL)材料。
发明背景
由于小切口白内障手术的最新进展,更加强调要开发适用于人造镜片的软质、可折叠材料。一般,此类材料是下列三种材料中的一种:水凝胶、硅氧烷和聚丙烯酸类。
一般,水凝胶材料具有相对低的折射率,要获得给定的折光能力需要更厚的镜片,因此,水凝胶比其它材料较少应用。硅氧烷材料通常具有比水凝胶高的折射率,但在以折叠状态被置于眼中后,趋向于突发性展开。突发性展开可能潜在地损坏内皮和/或者破坏天然的晶状体囊。聚丙烯酸类材料是合乎需要的,因为它们通常具有高的折射率并且比硅氧烷材料更慢或可控制地展开。
美国专利5,290,892公开了适合用作IOL材料的高折射率的聚丙烯酸类材料。这些聚丙烯酸类材料包含两种芳基丙烯酸类单体作为主要组分。它们也包含交联组分。由这些聚丙烯酸类材料制成的IOL可卷曲或折叠,通过小切口插入。
美国专利5,331,073也公开了软质聚丙烯酸类IOL材料。这些材料包含作为主要组分的两种丙烯酸类单体,该单体可由它们各自的均聚物的特性限定。第一种单体限定为:其均聚物的折射率至少为约1.50。第二种单体限定为:其均聚物的玻璃化转变温度低于约22℃。这些IOL材料也包括交联组份。此外,这些材料可任选地包含第四组分,该组分与前三个组分不同,它来自于亲水单体。这些材料优选具有总量小于约15重量%的亲水组分。
美国专利5,693,095公开了可折叠的眼科透镜材料,包括总量至少90重量%的仅仅两种主要的形成透镜的单体。一种形成透镜的单体是芳基丙烯酸类疏水单体。另一种形成透镜的单体是亲水单体。透镜材料也包括交联单体并且任选地包括UV吸收剂、聚合引发剂、活性UV吸收剂和活性蓝光吸收剂。
发明概述
现在已发现,改进的软质、可折叠的聚丙烯酸类材料特别适用于IOL,而且也可用作其它眼科或耳鼻喉科器件,如接触透镜、人工角膜、角膜环或嵌体、耳科通气管以及鼻植入物等。这些材料包含仅仅一种主要的形成透镜的组分:芳基丙烯酸类疏水单体。本发明的材料包括至少约80重量%的主要单体组分。该材料的其余部分包括交联单体和任选的一种或多种附加组分,其中附加组分选自UV-光吸收化合物和蓝光吸收化合物。
在其它因素中,本发明是基于这一发现:适用作可折叠IOL材料的丙烯酸类共聚物可用仅仅一种主要芳基丙烯酸类疏水单体合成,因此减少或消除了与固化共聚物有关的困难,如物理/化学不均匀性,其中该共聚物含有两种或两种以上主要的形成器件的单体。
本发明的详细描述
本发明的眼科或耳鼻喉科器件材料包括仅仅一种主要的形成器件的单体。为了方便起见,形成器件的单体可表达为透镜形成单体,特别涉及IOL时。但是,本发明的材料也适用作其它眼科或耳鼻喉科器件,如接触镜片、人工角膜、角膜嵌体或环、耳科通气管以及鼻植入物。
在本发明的材料中,芳基丙烯酸类疏水单体适合作为唯一的透镜形成单体,其分子式为:
其中:A是H、CH3、CH2CH3或CH2OH;
B是(CH2)m或[O(CH2)2]n;
C是(CH2)w;
m是2-6;
n是1-10;
Y不存在,或者Y是O、S或NR,前提是如果Y是O、S或NR,则B是(CH2)m;
R是H、CH3、CnH2n+1(n=1-10)、异-OC3H7、C6H5或CH2C6H5;
w是0-6,前提是m+w≤8;并且
D是H、C1-C4烷基、C1-C4烷氧基、C6H5、CH2C6H5或卤素。
用于本发明材料中的优选的芳基丙烯酸类疏水单体是那些,其中A是CH3,B是(CH2)m,m是2-5、Y不存在或Y是O,w是0-1以及D是H。最优选甲基丙烯酸(4-苯基丁基)酯、甲基丙烯酸(5-苯基戊基)酯、甲基丙烯酸(2-苄氧基乙基)酯以及甲基丙烯酸(3-苄氧基丙基)酯。
结构1的单体可由已知的方法制备。例如,所需单体的共轭醇可在反应器中与甲基丙烯酸甲酯、钛酸四丁基酯(催化剂)以及阻聚剂如4-苄氧基酚组合。然后加热反应器以促进反应,并且蒸馏出反应副产物使反应完成。另一种合成工艺包括将甲基丙烯酸加入共轭醇中并且用碳二亚胺催化,或者将共轭醇与甲基烯丙酰氯以及一种碱例如吡啶或三乙胺混合。
本发明的材料包括总量至少约80%,优选至少约85重量%或更多的主要的透镜形成单体。
本发明的共聚物材料是交联的。用于本发明共聚物的可共聚的交联剂可以是任何含有多于一个不饱和基团的末端烯属不饱和化合物。合适的交联剂包括,例如:二甲基丙烯酸乙二醇酯、二甲基丙烯酸二甘醇酯、甲基丙烯酸烯丙基酯、二甲基丙烯酸(1,3-丙二醇)酯、二甲基丙烯酸(2,3-丙二醇)酯、二甲基丙烯酸(1,6-己二醇)酯、二甲基丙烯酸(1,4-丁二醇)酯;CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2,其中n=1-50;以及CH2=C(CH3)C(=O)O(CH2)tO-C(=O)C(CH3)=CH2,其中t=3-20;及其相应的丙烯酸酯。最优选的交联单体是CH2=C(CH3)C(=O)O-(CH2CH2O)b-C(=O)C(CH3)=CH2,其中n是这样的数,使得数均分子量为约400,约600,或最优选为约1000。
所选择的交联剂应该能溶于所选择的结构1单体,以使固化问题降到最低程度。当n接近1-50范围的上限时,CH2=C(CH3)C(=O)O-(CH2CH2O)b-C(=O)C(CH3)=CH2交联剂在结构1的某些单体中可能达不到所要求的溶解程度,甚至在加热或声处理的辅助下也是如此。
一般,仅一种交联单体存在于本发明的器件材料中。然而在某些情况下,交联单体的组合也是所希望的。如果采用两种或更多交联剂的组合,则这些交联剂都不是CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2,其中n=2-50。
一般,交联组分的总量至少为0.1重量%,并且,根据其余组分的性质和浓度以及所要求的物理特性,该量可达20重量%。交联组分的优选浓度范围是0.1-15重量%。
除了芳基丙烯酸类疏水性透镜形成单体和交联组分外,本发明的透镜材料也可包含总量达到约10重量%的用于其它用途的附加组分,例如活性UV和/或蓝光吸收剂。
优选活性UV吸收剂是2-(2′-羟基-3′-甲代烯丙基-5′-甲基苯基)苯并三唑,商品名为O-Methallyl Tinuvin P(“oMTP”),可购自Polysciences公司(Warrington,宾夕法尼亚州)。UV吸收剂的通常用量为约0.1-5%(重量)。
合适的活性蓝光吸收化合物是美国专利5,470,932中所描述的那些,其整个内容引入本文以供参考。蓝光吸收剂的通常用量为约0.01-0.5%(重量)。
合适的聚合引发剂包括热引发剂和光引发剂。优选的热引发剂包括过氧化物自由基引发剂,例如叔丁基(过氧-2-乙基)己酸酯以及过氧二碳酸二-(叔丁基环己基)酯(商品名为Perkadox16,可购自Akzo化学品公司,Chicago,Illinois)。特别在透镜材料不含蓝光吸收生色团的情况下,优选的光引发剂包括苯甲酰基氧化膦光引发剂,例如蓝光引发剂2,4,6-三甲基-苯甲酰二苯基氧化膦,商品名为LucirinTPO,可购自BASF公司(Charlotte,North Carolina)。引发剂的通常用量为约5%(重量)或更少。
所述主要的透镜形成单体的性质和用量以及任何附加组分的性质和用量由成品眼科透镜所要求的性能所决定。优选,对组分及其比例进行选择,以便使本发明的丙烯酸类透镜材料具有以下特性,使得本发明的材料特别适用于要从5mm或更小的切口插入的IOL。
透镜材料优选在干态下具有至少为约1.50的折射率,此值由Abbe’折射仪在589nm(Na光源)测得。对于给定的镜片直径,由折射率低于1.50的材料制成的镜片必须比由较高折射率材料制成的能力相同的镜片更厚。因此,由折射率低于约1.50的材料制成的IOL镜片一般需要用于IOL植入的较大切口。
透镜材料的玻璃化转变温度(Tg),影响到材料的折叠和展开特性,优选低于约25℃,更优选低于约15℃。Tg由差示扫描量热仪以10℃/分钟速度进行测量,并且Tg值确定为热流曲线转折的中点。
透镜材料将具有至少150%的伸长率,优选至少为200%,最优选至少为300%。这一特性表明,透镜在折叠时一般不会龟裂、撕裂或破裂。聚合物样品的伸长率在哑铃状张力试验试样件上测定,该试样件总长20mm,柄部长4.88mm,总宽度为2.49mm,窄段宽度0.833mm,倒角半径8.83mm,厚度0.9mm。试验使用张力试验器在试件上进行,标准试验条件为23±2℃和50±5%相对湿度。夹具距离设置为14mm,十字头速度设置为500mm/分钟,并且将试件拉断。伸长率(应变)为拉断时的位移与最初夹具距离的比值。模量计算为,在选定的应变下,应力-应变曲线的即时斜率。应力计算为试件的最大载荷,通常为试件拉断时的载荷,假设最初面积维持不变。此应力在以下实施例中记录为“拉伸强度”。
本发明材料制成的IOL可具有能卷曲或折叠成可装入较小切口的小截面的任何设计。例如,IOL可具有称为一件或多件设计的形式,并且包括光学和触觉组件。光学组件是用作透镜的那部分。触觉组件附着于光学组件并且使光学组件固定在眼中的适当位置。光学和触觉组件可以由同样或不同的材料制成。多件透镜之所以如此称谓,是因为光学和触觉组件是分开制作的,然后将触觉部分附着于光学部分。在单件透镜中,光学和触觉部分由一块材料制成。基于这块材料,然后从该材料切出或用车床加工出触觉部分,以制成IOL。
本发明由以下实施例作进一步说明,这些实施例只用于说明,并不限制本发明。
实施例1:甲基丙烯酸(4-苯基丁基)酯的合成。
向含有被聚四氟乙烯树脂涂覆的电磁搅拌棒的三颈圆底烧瓶中依次装入120ml(1.09mol)甲基丙烯酸甲酯(2)、5.35g(0.015mol)四丁醇钛(Ti(OC4H9)4)、60ml(0.39mol)4-苯基-1-丁醇(1)以及14.6g(0.073mol)4-苄氧基酚(4-BOP)。将一只加料漏斗、温度计、一只带温度计的短路蒸馏头以及接收瓶装于三颈瓶颈中。将烧瓶置于油浴中并且升温,直到蒸馏开始。将甲基丙烯酸甲酯(2)装入加料漏斗中,以与馏出液同样的速度滴加。将反应混合物加热4小时,然后冷却至室温。粗产物被真空蒸馏,分离62.8g(0.29mol,74%)的甲基丙烯酸(4-苯基丁基)酯(3),其为透明无色的液体。
实施例2:甲基丙烯酸(3-苄氧基丙基)酯的合成。
向含有被聚四氟乙烯树脂涂覆的电磁搅拌棒的三颈圆底烧瓶中依次装入95ml(0.884mol)甲基丙烯酸甲酯(2),4.22g(0.012mol)四丁醇钛(Ti(OC4H9)4),50ml(0.316mol)3-苄氧基-1-丙醇(1)以及14.6g(0.073mol)4-苄氧基酚(4-BOP)。将一只加料漏斗,温度计、一只带温度计的短路蒸馏头以及接收瓶置于三颈烧瓶颈内。将烧瓶放入油浴中并且升温,直到蒸馏开始。将甲基丙烯酸甲酯(2)装入加料漏斗中,以与馏出液同样的速度滴加。将反应混合物加热4小时,然后冷却至室温。将粗产物真空蒸馏,分离36.5g(0.156mol,49%)甲基丙烯酸(3-苄氧基丙基)酯(3),其为透明无色的液体。
实施例3-29,如表1-4所示,说明本发明的材料。实施例3-29中每个配方如下制备。将表1-4所列配方组分混合后,每个配方经搅拌混合,然后注入聚丙烯25×12×1mm板模中。为了制板,用配料将板模底部的模腔填满,然后上盖封紧。充模可在惰性氮气下进行,也可在标准实验室大气下进行。为了在固化期间保持模具的几何形状,在模具上使用弹簧夹。夹紧的模具被置于强制空气炉中,通过加热到70-80℃,在70-80℃保持一小时,然后加热到约100-110℃并在约100-110℃下保持两小时进行固化。聚合结束时,打开模具,将固化的眼内透镜或聚合物板取出,用丙酮提取,以除去任何没有连接到交联网上的物质。
评价表1-4所示固化材料的物理特性数据(根据以上所述方法)。除非另作说明,以下所有组分的量均为重量%。下列缩写用于表1-4:
PEMA:甲基丙烯酸(2-苯乙基)酯
PPrMA:甲基丙烯酸(3-苯丙基)酯
PBMA:甲基丙烯酸(4-苯丁基)酯
BEEMA:甲基丙烯酸苄氧基乙氧基乙基酯
BEMA:甲基丙烯酸(2-苄氧基乙基)酯
BPMA:甲基丙烯酸(3-苄氧基丙基)酯
PPMA:甲基丙烯酸(5-苯基戊基)酯
BBMA:甲基丙烯酸(4-苄氧基丁基)酯
PEO 1000:聚乙二醇1000二甲基丙烯酸酯
PEO 600:聚乙二醇600二甲基丙烯酸酯
PEO 400:聚乙二醇400二甲基丙烯酸酯
EGDMA:二甲基丙烯酸乙二醇酯
t-BPO:叔丁基(过氧-2-乙基)己酸酯
BPO:过氧化苯甲酰
表1
实施例编号 | PEMA | PPrMA | PBMA | PEO1000 | EGDMA | t-BPO | %伸长率 | Tg(℃) |
3 | 85 | 15 | 1 | 304 | ||||
4 | 99 | 1 | 1 | 172 | 15 | |||
5 | 85 | 15 | 1 | 753 | -10 | |||
6 | 99 | 1 | 1 | 583 | 0 | |||
7 | 85 | 15 | 1 | 619 | -24 |
表2
组分 | 实施例 |
8 9 10 11 12 13 14 | |
BEMAPBMABPMAPPMABBMAPEO 1000EGDMAt-BPO拉伸强度(MPa)%应变杨氏模量(MPa)100%模量(MPa)RI(干) | - - - - - 89.9 -- - - - - - 90.094.7 90 - 99.6 - - -- - 89.7 - - - -- - - - 89.9 - -5.3 10 10.3 - 10.1 10.1 10.1- - - 0.4 - - -1.4 1.5 1.4 1.6 1.6 1.3 1.43.37 2.83 2.02 3.07 1.11 6.46 4.195900 659 515 974 440 815 6960.67 0.62 0.76 1.02 0.33 1.89 2.000.45 0.42 0.51 0.59 0.22 1.07 0.991.539 1.534 1.533 1.543 1.531 1.541 1.535 |
表3
组分 | 实施例 | ||||||||
15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | |
PBMA | 89.75 | 85.02 | 79.97 | 94.95 | 89.82 | 85.03 | 94.99 | 89.89 | 84.96 |
PEO 400 | 10.25 | 14.98 | 20.03 | --- | --- | --- | --- | --- | --- |
PEO 600 | --- | --- | --- | 5.05 | 10.18 | 14.97 | --- | --- | --- |
PEO 1000 | --- | --- | --- | --- | --- | --- | 5.01 | 10.11 | 15.04 |
BPO | 0.98 | 0.96 | 0.95 | 0.98 | 0.95 | 0.96 | 1.04 | 0.95 | 0.97 |
拉伸强度(MPA) | 8.23 | 8.6 | 8.74 | 6.55 | 6.33 | 514 | 6.17 | 5.62 | 4.35 |
%应变 | 444 | 378 | 325 | 881 | 707 | 562 | 1051 | 875 | 699 |
杨氏模量(MPA) | 6.59 | 5.78 | 5.56 | 3.85 | 2.82 | 1.77 | 4.05 | 1.92 | 1.24 |
100%模量(MPA) | 3.47 | 3.34 | 3.32 | 2.28 | 1.55 | 1.12 | 2.06 | 1.12 | 0.77 |
Tg(℃) | 5 | 4 | -1 | -1 | -5 | --- | --- | --- | --- |
表4
组分 | 实施例(组分以%w/w表示) | |||||||
24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | |
BEEMA | --- | --- | --- | --- | --- | --- | 99.6 | 90.0 |
PPrMA | 85.03 | --- | --- | 85.00 | --- | --- | --- | --- |
PBMA | --- | 85.02 | --- | --- | 84.94 | --- | --- | --- |
PPMA | --- | --- | 85.06 | --- | --- | 85.00 | --- | --- |
PEO 600 | 14.97 | 14.98 | 14.94 | --- | --- | --- | --- | --- |
PEO 1000 | --- | --- | --- | 15.00 | 15.06 | 15.00 | --- | 10.0 |
EGDMA | --- | --- | --- | --- | --- | --- | 0.6 | --- |
BPO | 1.00 | 1.01 | 0.99 | 1.01 | 1.01 | 1.01 | --- | --- |
t-BPO | --- | --- | --- | --- | --- | --- | 1.1 | 1.2 |
拉伸强度(MPA) | 8.34 | 4.24 | 2.67 | 6.15 | 3.35 | 2.05 | 1.56 | 1.22 |
%应变 | 502 | 486 | 390 | 662 | 582 | 402 | 468 | 294 |
杨氏(MPA) | 5.48 | 1.38 | 0.85 | 2.41 | 0.88 | 0.67 | 0.32 | 0.51 |
100%(MPA) | 3.09 | 0.96 | 0.57 | 1.41 | 0.63 | 0.48 | 0.24 | 0.36 |
Tg(℃) | --- | --- | --- | --- | --- | --- | -23.2 | -26.7 |
Claims (16)
1.一种聚合物眼科或耳鼻喉科器件材料,它具有至少150%的伸长率,包括一种单一的器件形成单体和一种交联单体,其中单一的器件形成单体的用量至少为80重量%并且是下式的芳基丙烯酸类疏水单体:
其中:
A是H、CH3、CH2CH3或CH2OH;
B是(CH2)m或[O(CH2)2]n;
C是(CH2)w;
m是2-6;
n是1-10;
Y不存在,或Y是O、S或NR,前提是如果Y是O、S或NR,则B是(CH2)m;
R是H、CH3、CnH2n+1(n=1-10)、异-OC3H7、C6H5或CH2C6H5;
w是0-6,前提是m+w≤8;并且
D是H、C1-C4烷基、C1-C4烷氧基、C6H5、CH2C6H5。
2.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中A是CH3,B是(CH2)m,m是2-5,Y不存在或Y是O,w是0-1以及D是H。
3.权利要求2的聚合物眼科或耳鼻喉科器件材料,其中芳基丙烯酸类疏水单体选自甲基丙烯酸(4-苯基丁基)酯、甲基丙烯酸(5-苯基戊基)酯、甲基丙烯酸(2-苄氧基乙基)酯以及甲基丙烯酸(3-苄氧基丙基)酯。
4.权利要求1的聚合物眼科或耳鼻喉科器件材料,进一步包括一种或多种组分,选自活性UV吸收剂和活性蓝光吸收剂。
5.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中所述材料为眼科器件材料并具有至少1.50的折射率。
6.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中所述材料的Tg低于+25℃。
7.权利要求6的聚合物眼科或耳鼻喉科器件材料,其中所述材料的Tg低于+15℃。
8.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中所述材料的伸长率至少为200%。
9.权利要求8的聚合物眼科或耳鼻喉科器件材料,其中材料的伸长率至少为300%。
10.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中所述器件选自接触透镜、人工角膜、角膜嵌体或环、耳科通气管以及鼻植入物。
11.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中交联组分包括一种或多种交联剂,选自二甲基丙烯酸乙二醇酯、二甲基丙烯酸二甘醇酯、甲基丙烯酸烯丙基酯、二甲基丙烯酸(1,3-丙二醇)酯、二甲基丙烯酸(2,3-丙二醇)酯、二甲基丙烯酸(1,6-己二醇)酯、二甲基丙烯酸(1,4-丁二醇)酯;CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2,其中n=1-50;CH2=C(CH3)C(=O)O(CH2)tOC(=O)C(CH3)=CH2,其中t=3-20;及其相应的丙烯酸酯,前提是如果器件材料包括两种或更多的交联剂,则这些交联剂都不是CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2,其中n=2-50。
12.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中单一的器件形成单体的用量为至少85重量%。
13.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中交联单体的用量为0.01-15重量%。
14.权利要求1的聚合物眼科或耳鼻喉科器件材料,其中芳基丙烯酸类疏水单体选自甲基丙烯酸(4-苯基丁基)酯、甲基丙烯酸(5-苯基戊基)酯、甲基丙烯酸(2-苄氧基乙基)酯以及甲基丙烯酸(3-苄氧基丙基)酯;交联单体是CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2,其中n是这样的数,使得交联单体的数均分子量为1000。
15.一种包括权利要求1中聚合物器件材料的眼内透镜镜片。
16.一种包括权利要求14中聚合物器件材料的眼内透镜镜片。
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2000
- 2000-08-23 CA CA002347707A patent/CA2347707C/en not_active Expired - Fee Related
- 2000-08-23 EP EP00957779A patent/EP1210380B1/en not_active Expired - Lifetime
- 2000-08-23 DK DK00957779T patent/DK1210380T3/da active
- 2000-08-23 WO PCT/US2000/023283 patent/WO2001018078A1/en active IP Right Grant
- 2000-08-23 AU AU69347/00A patent/AU766276B2/en not_active Ceased
- 2000-08-23 CN CNB008085501A patent/CN1151186C/zh not_active Expired - Fee Related
- 2000-08-23 PT PT00957779T patent/PT1210380E/pt unknown
- 2000-08-23 JP JP2001522299A patent/JP5459816B2/ja not_active Expired - Fee Related
- 2000-08-23 DE DE60018766T patent/DE60018766T2/de not_active Expired - Lifetime
- 2000-08-23 US US09/645,669 patent/US6528602B1/en not_active Expired - Lifetime
- 2000-08-23 BR BRPI0007069-6A patent/BR0007069B1/pt not_active IP Right Cessation
- 2000-08-23 AT AT00957779T patent/ATE291045T1/de active
- 2000-08-23 ES ES00957779T patent/ES2235935T3/es not_active Expired - Lifetime
- 2000-09-06 AR ARP000104653A patent/AR025571A1/es unknown
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2003
- 2003-01-24 US US10/350,993 patent/US6653422B2/en not_active Expired - Lifetime
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2011
- 2011-05-19 JP JP2011112886A patent/JP2011161261A/ja not_active Withdrawn
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- 2013-12-02 JP JP2013248836A patent/JP2014042846A/ja not_active Withdrawn
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CN1353726A (zh) | 2002-06-12 |
JP2011161261A (ja) | 2011-08-25 |
BR0007069A (pt) | 2001-07-31 |
DE60018766D1 (de) | 2005-04-21 |
AR025571A1 (es) | 2002-12-04 |
US20030130460A1 (en) | 2003-07-10 |
DK1210380T3 (da) | 2005-05-30 |
JP2014042846A (ja) | 2014-03-13 |
EP1210380B1 (en) | 2005-03-16 |
CA2347707A1 (en) | 2001-03-15 |
US6528602B1 (en) | 2003-03-04 |
JP5459816B2 (ja) | 2014-04-02 |
CA2347707C (en) | 2009-06-09 |
ES2235935T3 (es) | 2005-07-16 |
US6653422B2 (en) | 2003-11-25 |
WO2001018078A1 (en) | 2001-03-15 |
AU766276B2 (en) | 2003-10-16 |
JP2003508187A (ja) | 2003-03-04 |
DE60018766T2 (de) | 2005-08-11 |
EP1210380A1 (en) | 2002-06-05 |
BR0007069B1 (pt) | 2010-02-09 |
PT1210380E (pt) | 2005-05-31 |
ATE291045T1 (de) | 2005-04-15 |
AU6934700A (en) | 2001-04-10 |
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