CN1638879A - 为提高其韧性而填充了的硅树脂基复合材料 - Google Patents
为提高其韧性而填充了的硅树脂基复合材料 Download PDFInfo
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Abstract
通过在复合材料的每个纤维层之间掺入一种与所述基体树脂不同的坚韧性适当且较低模量的硅树脂来制造出具有更高抗分层能力的纤维增强硅基体树脂基复合材料。优选地，用预定的硅基体树脂浸渍的玻璃或碳纤维编织毡片被更坚韧的填充层硅树脂的前体涂布。树脂—纤维层和更坚韧的硅树脂填充层交替间隔所产生的叠合层提供了一种更坚韧的硅基复合材料。
Description
技术领域
本发明涉及硅树脂基复合材料。尤其是，本发明涉及，具有硬质硅基树脂的纤维增强型树脂复合材料，在该复合材料层中填充了柔性抗冲击材料的薄硅层。
背景技术
纤维增强的硅基树脂复合材料广泛应用于建筑构件中。纤维增强物经常采用编织的玻璃纤维毡片的形式。编织的碳纤维毡片提供更高模量的增强媒介，但是它们比玻璃纤维昂贵。其他纤维复合物例如芳族聚酰胺，尼龙，聚酯和石英纤维也可以采用。其他的纤维形式，例如非编织毡片和松散纤维层也可以用于硅基树脂复合材料中。
庞大的硅基树脂家族可适用于复合材料的应用。这样的树脂通常在固化形式中呈高度分支和交联的聚合物分子。它们基本上为硬质材料，具有高的弹性模量和高的弹性剪切模量。
这些纤维增强的以多层叠合形式存在的硅基树脂复合材料强度大并且防火，可以在例如飞机和轮船的内部应用。它们也可以用于电子业，例如要求具有挠曲强度和低重量的接线板和印刷电路板。
因此，层叠的硅树脂复合材料具有许多用途。然而，当它们承受压力至损坏时，这样的复合材料倾向于损坏发生在分层中。发生在基体树脂中的折裂位于增强纤维的各层之间。理想的是设计出一种对这样一种损坏模式具有更多抗性的纤维增强树脂复合材料。因此，本发明的目的之一是提供一种改进了的具有更高韧性和抗冲击性的硅树脂基层叠复合材料。
发明内容
本发明通过在叠合层分界面掺入坚韧的柔性硅树脂薄层来改进纤维毡片增强的硬质硅基树脂复合材料的制造。在基体树脂浸润的纤维毡片连续的各层被铺设时，一个合适的流动硅树脂的薄涂层被加入到各层之间，其韧度相对于硅基树脂的韧度来配制。优选的是，流动硅树脂被喷涂到每个浸润了的纤维层的一面上。填充或界面的树脂涂层的粘度要使之能够流动并且与树脂浸润的玻璃纤维毡片的表面完全贴合，例如，在叠合层之间提供基本上无气孔的层。优选地，填充的硅树脂被配制成在制造的叠层结构中的基体树脂固化期间固化。
合适的复合材料的硅树脂基体是可固化的异量分子聚合物，它们可以从化合物例如通常用的硅氧烷双官能和三官能结构单元生产出来。这些单元包括PhSiO3/2，MeSiO3/2，PhMeSiO2/2，Me2SiO2/2，ViMeSiO2/2，HMeSiO2/2，HPhSiO2/2，ViSiO3/2，ViMeSiO1/2，O1/2(Me2)Si-R-Si(Me2)O1/2以及类似物。这里Ph代表苯基基团，Me代表甲基基团，Vi代表乙烯基基团而R则代表二价碳氢化合物，例如亚苯基基团。适用于编织玻璃纤维毡片的基体树脂的一个例子是包含(PhSiO3/2)0.40(MeSiO3/2)0.45(Ph2SiO2/2)0.1(PhMeSiO2/2)0.05的硅烷醇基团。三官能单元的含量是这样的，即基体硅树脂基本上固化后为硬质，通常具有大于或等于0.67GPa的Young’s模量。其他合适的聚合物结构单元包括硅亚苯基树脂，亚甲基硅烷，硅乙烯以及类似物。硅基体树脂可以包括改性剂，例如直链或支链硅链段，以增加预定的有利于基体的物理性质。
由于成本和可利用率的原因，复合材料的纤维成分通常是玻璃或碳，但是其他纤维增强材料也适用于许多应用。例如，可以采用石英纤维和芳族聚氨酯，尼龙和聚酯纤维。编织玻璃纤维毡片通常被优选用于普通应用中，其中成本是一个重要的考虑因素。非编织纤维毡片和松散纤维层也可采用。
选择作为填充层材料的硅树脂将其特性补充给基体树脂。它比一般的硬质基体树脂更加坚韧。填充层树脂可以由类似硅氧烷部分合成，但是所形成的树脂要能够增加分层的韧性和抗性，并且增加复合材料的抗冲击强度。这样，填充层树脂通常包含比基体树脂更小份数的三官能硅基团并且将具有较低的Young’s模量，优选的小于或等于0.3GPa。可用于与上述基体树脂联合的填充层树脂的一个例子是具甲氧基功能的(PhSiO3/2)0.34(Me2SiO2/2)0.56(MeSiO3/2)0.1树脂。优选的是填充层树脂以薄的贴合膜施加于半固化的叠合层之间并且与基体树脂同时固化。
在大多数应用中，基体树脂浸润的纤维毡片的单层厚度为3至150密耳(mils)(大约75至3750微米)。填充的树脂厚度应该小得多，大约25至75微米。通常，半固化板的厚度是填充层树脂层厚度的3至50倍。结果，现有技术硅树脂叠层产品包含基体树脂浸渍的纤维层预订数量的层叠和塑形层。而本发明的叠层产品在半固化板的每一层之间包含相对薄的填充的硅树脂涂层。
由合适的填充层树脂所制成的复合材料的机械性质与类似的没有填充层硅树脂的复合材料相比表现出更高的韧性，并且没有过分丧失其强度和模量。优选的是，填充层树脂不导致热稳定性丧失或者能提高复合材料的温度特性。而没有或带有填充层树脂的复合材料的挠曲模量则是相当的。
具体实施方式
本发明的技术方案包括选择一种合适的硅基体树脂，一种合适的补充硅填充层树脂以及纤维状增强物。
当然，纤维状增强材料对于复合材料结构是必需的，但是它不是本发明使用的关键部分。玻璃纤维或碳纤维的编织毡片给予复合材料好的强度并且其编织结构易于用基体树脂前体浸渍和用填充层树脂前体涂布。其他形式和纤维复合物也可以采用而并不改变本发明的基本原则。
硅基体树脂的选择很大程度上是以已知的考虑因素为基础，即如何实现与特异性增强纤维相容以及所想得到的复合材料的特性。然而，填充层树脂是以它和基体树脂的相容性以及填充层树脂要使复合材料变坚韧的要求来进行选择的。通常，每个纤维增强物层将被处于相对低分子重量的非固化状态的基体树脂湿润并浸透。适当地配制这种前体树脂材料以便于它在通过采用热和压力来铺设半固化片层时是可固化的。类似地，填充层树脂的前体形式将优选地通过喷涂或其他涂布步骤被施加至半固化板的至少一面上。相应地，优选的是基体树脂和填充层树脂一起同时被固化。
如上所述，基体树脂和填充层树脂都可能包含硅氧烷基团或类似PhSiO3/2，MeSiO3/2，PhMeSiO2/2，Me2SiO2/2，ViMeSiO2/2，HMeSiO2/2，HPhSiO2/2，ViSiO3/2，ViMe2SiO1/2和O1/2(Me2)Si-R-Si(Me2)O1/2的单元。树脂的非固化形式可以包含硅氧烷基团或烷氧基基团以便通过凝结过程而被固化。或者前体树脂可以包含允许通过氢化硅烷化反应而固化的官能基团。
包括在后一组基团之中的合适的硅基体树脂是Katsoulis等人的，名称为“具有高强度和抗折韧性的硅倍半氧烷及其制备方法”的美国专利US6310146中所描述的硅倍半氧烷树脂。US6310146中的特征在此引入作为对这些可使用的硅树脂的充分描述。
如US6310146所述，基本的硅倍半氧烷树脂是一种氢化烷硅化反应的可固化异量分子聚合物树脂。它包含具有经验公式R1 aR2 bR3 cSiO(4-a-b-c)/2的单元，其中a为零或正数，b为零或正数，c为零或正数，并且0.8≤(a+b+c)≤3.0。而且，每个异量分子聚合物在每个分子上至少具有两个R1，并且每个R1基团是一个官能团，该官能团独立选自由氢原子和具有非饱和脂肪链的单价碳氢化物基团所组成的基团。每个R2和R3是独立选自由非官能基团和R1所组成的单价碳氢化物基团。
优选地，R1是一种链烯基基团，例如乙烯基或丙烯基。通常，R2和R3是非官能基团，选自由烷基和芳香基团所组成的基团。合适的烷基基团包括甲基，乙基，异丙基，n-丁基和异丁基基团。苯基基团是一种常用的芳香基团。除了以此特异性来鉴别的硅倍半氧烷异量分子聚合物之外，其他合适的硅倍半氧烷异量分子聚合物是(PhSiO3/2)0.75(ViMe2SiO1/2)0.25。
本发明的技术方案将通过以下实施例得以进一步的说明。
实施例1：制备玻璃纤维增强的硅树脂叠层产品
在本实施例中，制备的玻璃纤维增强的硅树脂叠层是用来作为根据本发明所制备的填充层复合材料的对照基础。
一种固体的，带有活性硅烷醇基团(大约2wt％)的低分子重量硅树脂被用作基体树脂。一种编织款式为7781并且带有热清洁表面(涂饰类型112)的商业化的玻璃纤维被用作制造叠层的增强物。硅树脂具有大约1400的数均分子量和大约1800的重均分子量。它通过剩余硅烷醇基团的凝结而得以固化。完全凝结的树脂复合物以通式(PhSiO3/2)0.4(MeSiO3/2)0.45(Ph2SiO2/2)0.1(PhMeSiO2/2)0.05来表示。
114克上述特征的未固化的树脂被溶解到96克甲苯中。以下固化材料被加入到树脂溶液中：0.144克Dow Corning Catalyst Y-177(一种包含锌辛酸盐和胆碱辛酸盐的商品材料)，7.2克聚合度为14的末端为三乙氧基甲硅烷氧基的聚二甲基硅氧烷，以及1.11克二丁基锡二月桂酸酯。
127克玻璃纤维，切成8个大小为“9×9”正方形片，用树脂溶液浸渍。浸渍了的纤维片被放到通风柜中的金属网的顶端过夜以便于使甲苯挥发。然后记录下干燥了的，树脂浸渍纤维片的重量并且将这些片以0/180°的方向(顶对顶，底对底)层叠至8层。层叠好的8层纤维—树脂复合材料随后被夹入到两块特氟龙涂布的平铝板之间并且在加热的压机中被固化。温度和压力循环如下。压机的温度以5°F/min的速度从室温上升至350°F。温度在180°F时被保持7分钟并带有最小压力。然后施加45磅/平方英寸(psig)的压力。温度维持在350°F一个小时。压力维持在45磅/平方英寸(psig)。随后压机以5°F/min的速度水冷却至100°F同时维持压力在45磅/平方英寸(psig)。
固化的叠层从压机中取出并被放入一个空气循环烤箱中在400°F下进行后熟化，或者更高至500°F，持续一个小时。关上烤箱并让叠层在烤箱中冷却至室温。
然后将叠层称重并且树脂含量预定在大约40wt％。
几个例子以相同的方式制备并且其屈服延伸率，挠曲强度，挠曲模量和冲击能量根据如下所述的检测程序来决定。各个检测的平均值见随后表中以实施例1为标题的横行中。
实施例2 制备硅橡胶填充的玻璃纤维增强的硅树脂叠层产品
在本实施例中，一种玻璃纤维增强的硅树脂复合材料根据本发明通过填充入坚韧的硅树脂而被制备。
在实施例1中的特异性树脂复合物被用作基体树脂。同样的编织款式为7781并且涂饰类型为112的玻璃纤维被用作增强材料。114克未固化的树脂被溶解到96克甲苯中。与实施例1一样，0.144克Dow Corning Catalyst Y-177，7.2克聚合度为14的末端为三乙氧基甲硅烷氧基的聚二甲基硅氧烷，以及1.11克二丁基锡二月桂酸酯被加入到溶液中并混合在一起。
与实施例1一样，127克玻璃纤维，切成8个大小为“9×9”正方形片，用树脂溶液浸渍。浸渍了的纤维片被放到通风柜中的金属网的顶端干燥过夜。然后记录下干燥了的树脂浸渍的纤维片的重量。
一个大约2密耳厚的Dow Coring 1-2577保形的硅树脂涂层通过在表面喷涂10wt％的保形涂层溶液而被施加到浸渍了的纤维的一面上。保形涂层的稀释溶剂为甲苯。涂层为甲氧基官能(PhSiO3/2)0.34(Me2SiO2/2)0.56(MeSiO3/2)0.1树脂。喷涂过的浸渍了的纤维被放置12小时以便干燥。这些片被再次称重并且以0/180°的方向层叠至8层。层叠的纤维—树脂复合材料随后被夹入到两块特氟龙涂布的平铝板之间并且在加热的压机中被固化。
压机操作的温度和压力循环与实施例1相同并如下所示。压机的温度以5°F/min的速度从室温上升至350°F。温度在180°F时被保持7分钟并带有最小压力。然后施加45磅/平方英寸(psig)的压力。温度维持在350°F一个小时。压力维持在45磅/平方英寸(psig)。随后压机以5°F/min的速度水冷却至100°F同时维持压力在45磅/平方英寸(psig)。
固化了的带填充层的叠层从压机中取出并被放入一个空气循环烤箱中在400°F下进行后熟化，持续一个小时。然后，关上烤箱并让叠层在烤箱中冷却至室温。
然后将叠层称重并且树脂含量预定在大约40wt％。
几个例子以相同的方式制备。填充层的涂层通过喷涂而施加。涂层非常薄，但是实验性的喷涂程序无需产生均匀的填充层厚度。每个样本的屈服延伸率，挠曲强度，挠曲模量和冲击能量根据如下所述的检测程序来决定。屈服延伸和挠曲检测的平均值见随后表中以实施例2为标题的横行中。然而，由于薄的填充层涂层的厚度不同的变化，所得到的冲击能量范围也在表格中说明。看起来所有的填充层样本冲击能量值基本上都大于现有技术，即实施例1样本的冲击能量值。一些填充层样本几乎是实施例1样本的冲击能量值的两倍。
挠曲检测
检测采用一台8520型英斯特朗拉伸强度试验机和一个100Ib的测力元件按照ASTM790(美国材料试验学会标准编号790)进行。十字头率为4mm/min。样本大小为“1×4”并且8层厚。采用的取值范围为50mm。样本是采用水冷却的金刚石锯从叠层上切割下来的，并且在80℃下干燥，检测前要在检测条件下至少平衡24小时。从这个检测中可以得到Young’s模量，挠曲强度以及挠曲延伸率。以每单位体积样本在断裂前的能量吸收值作为韧性值。
冲击检测
检测采用一台G检测方法的冲击检测仪按照ASTM790(美国材料试验学会标准编号790)进行。样本采用水冷却的金刚石锯切割成“2×2”大小，在如上段落中所述的条件下干燥并且在检测之前同样进行条件平衡。以能够导致统计学上可识别的损坏时的能量水平作为冲击能量。
对照：
| 样本 | 玻璃重量百分比Wt％ | 屈服延伸率％ | 挠曲强度ksi | 挠曲模量ksi | 冲击能量in.Ib |
| 实施例1 | 60 | 1.70±0.42 | 24.66±0.22 | 1835±142 | 23.5±0.7 |
| 实施例2 | 60 | 1.72±0.36 | 16.50±0.60 | 1487±73 | 26.0-46.0 |
至此，本发明采用编织玻璃纤维毡片进行举例说明，但是其他合适的纤维复合物以及形式也可以用于本发明的技术方案中。实施例是在这种特异性的背景下选择的。类似的其他硬质硅基体树脂和柔性硅填充层树脂也可以采用。
因此，本发明虽然采用一些示意性实施例加以描述，但是明显的是本领域技术人员能够很容易的采用其它的形式。因此，本发明的保护范围仅由权利要求书来限制。
Claims (11)
1、一种纤维增强的硅基体树脂复合材料包括多层纤维，每层用所述的硬质硅基体树脂浸渍，在这样的每层基体树脂浸渍的纤维之间带有一个比所述基体树脂弹性模量更低和韧性更高的硅树脂填充层。
2、一种如权利要求1所述的纤维增强的硅基体树脂复合材料，其中所述硅基体树脂的Young’s模量等于或大于0.67GPa并且所述填充的硅树脂的Young’s模量小于或等于0.3GPa。
3、一种如权利要求1或2所述的纤维增强的复合材料，其中所述的纤维层包含编织的纤维毡片，其材料选自由芳族聚酰胺树脂，聚酯树脂，尼龙树脂，碳，玻璃或石英所组成的组中。
4、一种如权利要求1-3所述的纤维增强的复合材料，其中所述的硅基体树脂包含硅氧烷部分，该部分选自由PhSiO3/2，MeSiO3/2，PhMeSiO2/2，Me2SiO2/2，ViMeSiO2/2，HMeSiO2/2，HPhSiO2/2，ViSiO3/2，ViMeSiO1/2和O1/2(Me2)Si-R-Si(Me2)O1/2组成的组中，其中Ph代表苯基基团，Me代表甲基基团，Vi代表乙烯基基团而R则代表二价碳氢化合物。
5、一种如权利要求1-3所述的纤维增强的复合材料，其中所述的硅基体树脂固化前包含硅烷醇基团，该基团含有(PhSiO3/2)0.40(MeSiO3/2)0.45(Ph2SiO2/2)0.1(PhMeSiO2/2)0.05。
6、一种如权利要求1-3所述的纤维增强的复合材料，其中所述的填充的硅树脂包含硅氧烷部分，该部分选自由PhSiO3/2，MeSiO3/2，PhMeSiO2/2，Me2SiO2/2，ViMeSiO2/2，HMeSiO2/2，HPhSiO2/2，ViSiO3/2，ViMeSiO1/2和O1/2(Me2)Si-R-Si(Me2)O1/2组成的组中，其中Ph代表苯基基团，Me代表甲基基团，Vi代表乙烯基基团而R则代表二价碳氢化合物。
7、一种如权利要求1-3所述的纤维增强的复合材料，其中所述的填充的硅树脂在固化前包含具甲氧基功能的(PhSiO3/2)0.34(Me2SiO2/2)0.56(MeSiO3/2)0.1树脂。
8、一种如权利要求1-3所述的纤维增强的复合材料，其中所述的填充的硅树脂是通过将所述树脂的前体喷涂到硅基体树脂浸渍了的所述纤维层的每一层的表面上，然后使所述填充的硅树脂和所述的硅基体树脂同时固化而形成的。
9、一种制造纤维增强的硅基体树脂复合材料的方法，所述方法包括将至少一层增强纤维用可固化的硅基体树脂浸渍从而形成多个基体树脂涂布的纤维层，所述硅基体树脂固化后基本上是硬质的；
在所述基体树脂涂布的纤维层的每层的一面上喷涂一层可固化的硅树脂作为基本上共延伸的柔性涂层，其厚度比所述基体树脂涂布的纤维层薄，所述喷涂的硅树脂固化后具有比所述固化的硅基体树脂更低的Young’s模量；层叠多个所述喷涂了的基体树脂涂布的纤维层，并且在固化所述树脂以形成所述硅基体树脂复合材料时用所述的较低模量硅树脂的填充层对所述层进行塑形。
10、一种如权利要求9所述的方法，其中所述硅基体树脂的Young’s模量等于或大于0.67GPa，而所述填充的硅树脂的Youngg’s模量小于或等于0.3GPa。
11、一种如权利要求9所述的方法，其中所述的填充的硅树脂包含硅氧烷部分，该部分选自由PhSiO3/2，MeSiO3/2，PhMeSiO2/2，Me2SiO2/2，ViMeSiO2/2，HMeSiO2/2，HPhSiO2/2，ViSiO3/2，ViMeSiO1/2和O1/2(Me2)Si-R-Si(Me2)O1/2组成的组中，其中Ph代表苯基基团，Me代表甲基基团，Vi代表乙烯基基团而R则代表二价碳氢化合物。
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| CA (1) | CA2477948C (zh) |
| DE (1) | DE60332995D1 (zh) |
| WO (1) | WO2003078079A1 (zh) |
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| CN101675096B (zh) * | 2007-05-01 | 2012-12-26 | 陶氏康宁公司 | 纳米材料填充的有机硅组合物和增强的有机硅树脂膜 |
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| CN104603187B (zh) | 2012-09-07 | 2018-02-02 | 通用电气公司 | 用于制造离子交换膜的方法 |
| US10046538B2 (en) * | 2013-07-26 | 2018-08-14 | Samsung Sdi Co., Ltd. | Composite sheet, method for manufacturing same, and display device including same |
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| US3472730A (en) * | 1967-12-28 | 1969-10-14 | Minnesota Mining & Mfg | Heat-curable filament-reinforced resinous sheeting and laminating process using same |
| US4539253A (en) * | 1984-03-30 | 1985-09-03 | American Cyanamid Co. | High impact strength fiber resin matrix composites |
| JPS61172736A (ja) * | 1985-01-29 | 1986-08-04 | 平岡織染株式会社 | 難燃性シ−ト材料 |
| US4842670A (en) * | 1986-03-07 | 1989-06-27 | Northrop Corporation | Molded vacuum bag for debulking and autoclaving laminates of complex shapes |
| US4957801A (en) * | 1989-05-17 | 1990-09-18 | American Cyanamid Company | Advance composites with thermoplastic particles at the interface between layers |
| GB9114526D0 (en) | 1991-07-05 | 1991-08-21 | Dow Corning Sa | Compositions and use thereof |
| US5322727A (en) * | 1992-10-21 | 1994-06-21 | Alliedsignal Inc. | Plasma spray masking tape |
| EP0850998B1 (en) * | 1996-12-31 | 2004-04-28 | Dow Corning Corporation | Method for making rubber-modified rigid silicone resins and composites produced therefrom |
| US5830950A (en) | 1996-12-31 | 1998-11-03 | Dow Corning Corporation | Method of making rubber-modified rigid silicone resins and composites produced therefrom |
| US5747608A (en) | 1996-12-31 | 1998-05-05 | Dow Corning Corporation | Rubber-modified rigid silicone resins and composites produced therefrom |
| FR2787461B1 (fr) * | 1998-12-22 | 2001-01-19 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation a temperature ambiante et/ou a chaud pour former des elastomeres |
| US6310146B1 (en) | 1999-07-01 | 2001-10-30 | Dow Corning Corporation | Silsesquioxane resin with high strength and fracture toughness and method for the preparation thereof |
-
2002
- 2002-03-12 US US10/095,506 patent/US6660395B2/en not_active Expired - Fee Related
-
2003
- 2003-02-20 JP JP2003576123A patent/JP4082456B2/ja not_active Expired - Fee Related
- 2003-02-20 EP EP20030709254 patent/EP1485251B1/en not_active Expired - Lifetime
- 2003-02-20 CN CNB038056445A patent/CN1311914C/zh not_active Expired - Fee Related
- 2003-02-20 WO PCT/US2003/005358 patent/WO2003078079A1/en active Application Filing
- 2003-02-20 AU AU2003213208A patent/AU2003213208A1/en not_active Abandoned
- 2003-02-20 CA CA 2477948 patent/CA2477948C/en not_active Expired - Fee Related
- 2003-02-20 AT AT03709254T patent/ATE471216T1/de not_active IP Right Cessation
- 2003-02-20 DE DE60332995T patent/DE60332995D1/de not_active Expired - Lifetime
- 2003-02-20 KR KR1020047013745A patent/KR100975275B1/ko not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101473448B (zh) * | 2006-04-18 | 2011-05-11 | 道康宁公司 | 硒化铟铜基光伏器件及其制造方法 |
| CN101681939A (zh) * | 2006-06-05 | 2010-03-24 | 陶氏康宁公司 | 包括有机硅树脂层的太阳能电池 |
| CN101913276A (zh) * | 2010-07-07 | 2010-12-15 | 电子科技大学 | 一种聚芳醚腈树脂和纤维布的层压复合材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1485251B1 (en) | 2010-06-16 |
| ATE471216T1 (de) | 2010-07-15 |
| CN1311914C (zh) | 2007-04-25 |
| EP1485251A4 (en) | 2006-04-05 |
| CA2477948C (en) | 2011-10-18 |
| DE60332995D1 (de) | 2010-07-29 |
| US20030175533A1 (en) | 2003-09-18 |
| JP4082456B2 (ja) | 2008-04-30 |
| JP2005520020A (ja) | 2005-07-07 |
| KR20050004791A (ko) | 2005-01-12 |
| WO2003078079A1 (en) | 2003-09-25 |
| US6660395B2 (en) | 2003-12-09 |
| EP1485251A1 (en) | 2004-12-15 |
| AU2003213208A1 (en) | 2003-09-29 |
| CA2477948A1 (en) | 2003-09-25 |
| KR100975275B1 (ko) | 2010-08-12 |
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