CN1146381C - 生物活性复合材料及其制备方法 - Google Patents
生物活性复合材料及其制备方法 Download PDFInfo
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- CN1146381C CN1146381C CNB998116149A CN99811614A CN1146381C CN 1146381 C CN1146381 C CN 1146381C CN B998116149 A CNB998116149 A CN B998116149A CN 99811614 A CN99811614 A CN 99811614A CN 1146381 C CN1146381 C CN 1146381C
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- 230000000975 bioactive effect Effects 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 32
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 31
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 29
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 25
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 24
- 238000000280 densification Methods 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
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Abstract
本发明涉及制备基于磷灰石的、主要在牙科和整形术应用中起支持功能的、改进的生物活性复合材料的方法，包括依据在其制备过程中材料的反应倾向调节封闭温度和在封闭体系中的施加压力，和通过加入辅助剂来进一步阻碍反应倾向和分解倾向。
Description
技术领域
本发明涉及用于制备含有在材料制备时有分解倾向的化合物(相)的生物活性材料的最佳条件。本发明具体涉及用作稳定的医用植入物的材料。
发明背景
具有生物活性的材料通常含有不同性质的相。具体而言，所包含的任何相在制备期间都可能有发生分解的明显倾向，例如金属和尤其是陶瓷在高温下会发生分解。该开始的热激活分解可能对最终产品有直接的消极影响，例如形成气体化合物，气体化合物形成孔，这些孔成为了产品的缺点，尤其从外观上看更是如此，或者导致形成新的不需要的相。相关影响是，有分解倾向的相的分解被存在的另一相、例如在一定温度下导致分解的氧化物催化，从而使得具有分解倾向的相应纯材料的分解显著减少。为了改善与纯磷灰石有关的机械性质，在生物活性复合材料中存在氧化物或金属是必需的。
其它不涉及本申请基本内容的相关方面除了在文献中以外还在下述专利/专利申请中描述过：US 3789900、DE 330122、US4149893、US 4957674、US 4599085、DE 2928007 A1和JP 62-142565。
发明描述
本发明涉及复合材料及其制备方法，所述复合材料包含至少一个化学较不稳定相，并具体涉及稳定的陶瓷植入物材料。
本发明的目的是提供在牙科或整形术应用中具有支持功能、并具有最佳性质的生物活性材料、尤其是植入物材料，所述材料是通过使用其中对所包含的化学较不稳定的生物活性相作了特别考虑的制备方法制得的。本发明的关键方面涉及非活性相与活性(生物功能)相之间的反应，和如何减小或消除或控制这些不需要的反应。已经建立了关于复合材料中的分解的新理论模型，该模型与依据本发明所获得的结果一致。
本发明提供了如本申请权利要求书所述的材料及其制备方法。
本发明复合材料包含磷灰石，其中磷灰石含量低于90vol％、优选5-80vol％、更优选10-50vol％、最优选25-45vol％。磷灰石相可以是纯的羟基磷灰石或磷灰石相混合物，即羟基磷灰石与氟磷灰石的混合物。本发明复合材料中的生物惰性基质优选为结构陶瓷，优选一种或多种氧化物，例如氧化铝、氧化锆、和/或氧化钛。结构陶瓷的含量可以为10-95vol％、优选为40-95vol％、更优选为55-85vol％，并且可适当地在材料中占多数。或者，生物惰性基质可以是以相同浓度存在的结构金属，优选为基于Fe或Co-Cr的、或者基于Ti、Ta或Zr的结构金属。除了磷灰石和生物惰性基质外，本发明材料还可以包含少量(优选低于10vol％)其它相。
现在已经惊奇地发现(与本发明有关)，在氧化物-羟基磷灰石体系中磷灰石分解的反应机制不是依据文献中记载的传统方式进行的，而是分两步进行，其中羟基磷灰石，OHAp＝Ca10(PO4)6(OH)2，中的OH首先离开结构，在原处留下空位。当空位的数目超过一定临界水平时，缺损的OHAp可继续与催化分解反应的周围化合物(例如Al2O3)反应。这两步反应是
这类分解在材料的致密化/烧结时发生。通过改变反应平衡可防止分解，这可通过3条主要不同途径进行，即降低封闭系统的温度、提高压力和/或特意加入活性化合物分解所形成的化合物。这使得在本发明材料的致密化/煅烧/烧结过程中，应当使用低的烧结温度，封闭必须在实际烧结过程开始之前早先进行，并且在致密化开始之前给包套施加外部机械压力。此外，应当维持初始施用的压力、即在致密化开始前施用的压力以作为连续致密化期间的最小压力水平，也就是说在连续致密化/烧结期间压力通常不应当降至初始压力以下，而是应当逐渐提高压力。
在本发明方法中，首先通过例如冷等静压压制(CIP)或其它成形法将磷灰石与氧化物或金属的粉末混合物适当地成形，获得生压坯。然后，将生压坯致密化/烧结，所采用的合适方法是在耐气体高压的封闭室中进行热等静压压制(HIP)或烧结，气体超压烧结(GPS，气体压力烧结)。在热等静压压制的情况下，将生压坯置于预成形的包套中，然后将包套密封。周围气体给包套施加了压力，包套把压力传递给生压坯，从而将其致密化。相反，在超压烧结的情况下，生压坯是与气体直接接触。在这两种烧结技术中，可使用环绕在生压坯周围的一些类型的阻挡层或粉末垫。依据本发明，可向这些辅助层中加入能分解和形成阻碍磷灰石分解的化合物的化合物例如水合物、或者能防止金属(对于金属磷灰石组合物)被化学攻击的化合物。
依据本发明，系统/包套的封闭和施加压力应当在磷灰石相开始实质分解前进行，即在显著低于烧结所采用的最终温度的温度下进行。在某些情况下，施加压力可以在室温进行，并且通常在低于900℃的温度进行，对于基于陶瓷的复合材料，优选在低于800℃、更优选低于700℃的温度进行，对于基于金属的复合材料，优选在低于500℃的温度进行。初始施加的压力可以是完全的或部分的，即施加的压力水平可以等于终压力或者可以小于终压力。对于HIP，终压力通常非常高，最经常超过100Mpa，高达200MPa或甚至更高。在封闭室中烧结时，气压通常为最高100-200atm，即10-20Mpa。初始压力可以为10MPa或低至约0.2MPa。在较低温度下，采用低初始压力的目的主要是防止包套材料在由于温度增高所导致的高压(根据理想气体定律)或者由于特意加入的化合物开始分解出气体化合物、优选蒸汽所导致的高压下的膨胀。然而，0.2MPa-终压力的初始部分压力水平也是可行的。根据复合材料体系的类型、粉末类型(粒径和形态)、所加工的量、特意加入的额外分解性化合物以及包套类型和烧结技术来恰当地选择所用压力。对于基于氧化物的材料，终温度一般为至少900℃、通常为至少1000℃、最经常至少1100℃。对于基于金属的材料，终温度较低，一般为约500-800℃，通常为600-800℃。终压力和终温度通常维持约1-2小时。
依据本发明一个方面，施加压力和提高温度是逐步进行的。这样做的目的是按照需要施加增加的压力梯度和提高温度。在室温施加的、并且可维持在例如0.2-5MPa水平的第一初始压力可因此具有稳定包套的目的。当此后提高温度时，包套中的压力会依据理想气体定律而增加。在低于磷灰石相开始分解的温度水平的温度下，作为分解性化合物额外加入的辅助剂可能开始分解(见下文)，也导致包套中的压力增加。这两方面结合起来需要作为反压的高压力水平，例如约1-10MPa。最后，当达到其中生压坯自身的材料－磷灰石相可以开始分解的温度水平时(见上述温度水平)，施加所需的终压力以阻止这种分解。然后将温度提高至所需终温度并维持以进行烧结。如何恰当地进行逐步压力施加取决于复合体系类型、粉末类型(粒径和形态)、所加工的量、特意加入的额外分解性化合物以及包套类型和烧结技术。
热等静压压制(HIP)在陶瓷生产中的应用当然是已知的，并且瑞典专利465571中还描述了其在氧化物-磷灰石体系中的应用。然而，在这些文献中没有描述自身包套性能—封闭和早期施加压力或者加入在阻挡层中的辅助剂—仅描述了在其致密化时所采用的温度和压力。在烧结时为了能防止分解和不需要的反应，还必须考虑进行实际热等静压压制(致密化)的步骤，并且依据本发明进行该步骤，其中在实际烧结前的温度间隔中，调节封闭时的温度和给包套施加压力时的温度(或者气压(对于GPS的情况))以使其与存在相的分解倾向相适应。如WO-A1-9410100中所述的仅作为用于多孔磷灰石的部分方法的等静压压制并不能导致形成致密的稳定磷灰石，尤其是不能导致形成具有高度稳定性的磷灰石生物复合材料，其中与纯磷灰石相比，这样制得的复合材料在相当低的温度下发生分解，这是因为氧化物催化了分解所致。见实施例1中的结果。必须根据不同氧化物-磷灰石体系在低于W0-A1-9410100中给出的温度下的分解倾向来施加压力。
依据本发明另一方面，可在封闭体系中加入额外的分解性化合物，这种化合物能产生复合材料体系(主要是磷灰石相)将分解成的化合物。因此就另外阻碍了复合材料的分解。在特别的实施方案中，除了早期封闭和早期逐步施加压力之外，还加入粉末形式的分解辅助化合物，这种化合物能早期形成实际组分中功能相将分解成的多相或任何一相。对于含有金属和功能相(磷灰石)的复合材料，可加入能降低金属反应—主要是氧化反应的另一辅助剂。当致密化通常在比陶瓷所用的温度要低的温度下进行时，金属通常是反应性更强的相。在这些情况下，辅助剂有利地为金属细小粉末，例如细铁粉或细钛粉，它们减少了环绕在复合材料周围的气体环境中的氧含量。有利起见，可将抗活性相分解的辅助化合物和保护金属相的辅助剂加到在加工期间环绕在组分周围的阻挡层或粉末垫中。为了防止磷灰石相分解，可将易于释放出羟基和形成蒸汽以及其它物质(碳酸盐、磷酸盐等)的不同类型水合物作为辅助剂加到阻挡层或粉末垫中。以该方式用作辅助剂的材料通常是具有下述功能的水合物(例如水合粘固剂或包含结晶水的盐)：在比氧化物-磷灰石体系中开始分解反应的温度低的温度、即至少低于900℃、优选低于800℃、甚至更优选低于600℃的温度释放出水。在使用时，辅助剂的浓度通常比较低，并且调节其浓度以使得与体系和加工的材料的量相适应。在粉末垫中，辅助剂的浓度一般低于或等于10vol％，在阻挡层中一般低于约5vol％。
下面通过多个实施例描述本发明。
实施例1
下图显示了水是如何脱离纯羟基磷灰石(OHAp)和复合材料(包含60vol％羟基磷灰石的氧化铝)中的羟基磷灰石的实例。
导致脱水差异的原因是分解，对于复合材料，脱水是依据反应1和2(见上文)以顺续步骤进行的，而对于纯羟基磷灰石，脱水是依据反应1进行的。氧化物的存在加快了羟基的脱离。该曲线图是通过在Setaram TAG24牌TG仪器中进行热重量分析而绘制的。
实施例2
将包含45vol％羟基磷灰石粉末的四角形稳定的氧化锆粉末(TZ)进行热等静压压制，其中采用不同的封闭和压力施加，但是具有相同终参数，即1200℃和200MPa 1小时。在第一种情况(TZ-HAI)中，将玻璃包套材料在900-950℃封闭，并且在1150℃施加全部压力。在第二种情况(TZ-HA II)中，在室温封闭，并施加约5atm的超压直至温度升到650℃，在该温度施加80atm压力。在800℃施加160MPa的压力，当温度升至最高温度时终压力为190MPa。用扫描电子显微镜分析微结构，结果表明TZ-HA I包含多个非常小的孔，同时有部分四角形相转化成了立方体相，这是因为HA已经分解成了TCP-Ca3(PO4)2。孔很可能是由于OH基离开所致。对于TZ-HA II，获得了完全致密的材料，仍然保持四角形结构，该结构具有良好强度并抗断裂。作为粘固剂，HA分解成TCP—释放CaO和导致四角形相转化成了立方体相—在更粗糙的微结构中难以检测到，这是因为分解反应是在TZ与HA之间的边界线进行的，反应量取决于微结构(TZ颗粒与HA颗粒的分布以及颗粒大小)。
实施例3
将二氧化钛与羟基磷灰石(HA)混合，并在具有Sialon碾磨体和异丙醇(作为溶剂)的球磨机中研磨4天。将溶剂在封闭通风橱内的烘箱中于90℃蒸发掉，最后在450℃干燥2小时。HA含量为30vol％。采用不同的封闭和压力施加，将样本进行热等静压压制。在测试A中，在室温进行封闭，并施加3atm的超压，将该压力维持至700℃，在该温度施加160MPa的终压力，将温度升至900℃并维持恒定1小时。在测试B中，直接在900℃进行封闭和施加160MPa的终压力，并维持1小时。测试A样本含有所需的相金红石和HA，而测试B的结果表明有一些分解，并形成了钛酸盐-CaTiO3和TCP-Ca3(PO4)2。没有检测到任何值得一提的孔隙。用X-射线衍射经由相分析的检测可能性也取决于HA和微结构。然而，形成钛酸盐的倾向很明显。一般来说，当复合材料中HA含量低于约20vol％时就难以检测到HA的分解。
实施例4
依据实施例2中描述的方法将氧化铝与羟基磷灰石混合。HA含量为45vol％。通过下述方法将样本致密化：在1200℃、25MPa压力下热压(HP)2小时，或者进行热等静压压制(HIP)，其中是在700℃施加全部压力-160MPa，并将温度升至1200℃、维持2小时。在热压样本中，表现出HA分解成TCP-Ca3(PO4)2，而热等静压压制样本表现出含有氧化铝和HA的正确相。
实施例5
依据实施例2，将细钢粉316L与40vol％羟基磷灰石(HA)混合，与实施例2不同之处在于，溶剂是在200℃真空除去的。将材料、冷等静压压制体置于包套中以进行热等静压压制，将包套在真空下封闭。在600℃施加160MPa的终压力，并维持1小时。微结构分析(SEM)与相分析(X-射线衍射)表明，在终产品中存在含有维持HA相的完全致密材料。其中氮化硼阻挡层中已经加入了额外的由316L组成的细金属粉末，所述金属粉末浓度为10vol％，是通过在研磨条件下混合2天而细粉碎的。
Claims (21)
1.制备包含磷灰石的牙科或整形术用生物活性复合材料的方法，所述材料包含当将材料在高温、一定压力下致密化时有分解倾向的基团，所述基团是羟基、碳酸根、磷酸根、卤素或其组合，所述材料还包含结构陶瓷，其浓度为10-95vol％，所述方法的特征在于，在封闭体系中进行致密化，其中在达到大于900℃的致密化的终温度之前，在低于900℃的温度下，并且在磷灰石相开始实质分解之前施加部分或全部压力。
2.权利要求1的方法，其特征在于所述结构陶瓷是氧化物。
3.权利要求2的方法，其特征在于所述氧化物为氧化铝、氧化锆或氧化钛。
4.权利要求1或2的方法，其特征在于所述结构陶瓷浓度为40-95vol％。
5.权利要求4的方法，其特征在于所述结构陶瓷浓度为55-85vol％。
6.权利要求1或2的方法，其特征在于，所述复合材料包含浓度为5-80vol％的羟基磷灰石和/或其它磷灰石。
7.权利要求6的方法，其特征在于所述磷灰石浓度为10-50vol％。
8.权利要求7的方法，其特征在于所述磷灰石浓度为25-45vol％。
9.权利要求1或2的方法，其特征在于，所述封闭体系和施加压力在低于800℃的温度进行。
10.权利要求9的方法，其特征在于所述封闭体系和施加压力在低于700℃的温度进行。
11.权利要求1或2的方法，其特征在于进行所述材料致密化的终温度为1000℃以上，并且终压力为100Mpa以上。
12.权利要求11的方法，其特征在于，进行所述材料致密化的终温度为1100℃以上。
13.权利要求11的方法，其特征在于，终压力为200MPa以上。
14.权利要求1或2的方法，其特征在于，在达到致密化的终温度之前、和磷灰石相开始分解之前施加的压力是以施加部分压力的方式进行的，由此施加的部分压力为0.2-10MPa。
15.权利要求1或2的方法，其特征在于，所述材料的致密化是逐步式进行的，施加第一部分压力，该第一部分压力为0.2-5MPa，并维持该压力直至第一个温度，然后施加第二个部分压力，该第二部分压力为1-10MPa，并维持该压力直至第二个温度，之后施加可能的进一步压力和温度，或者施加终压力和终温度。
16.权利要求1或2的方法，其特征在于，在通过热等静压压制进行的致密化情况下向阻挡层中加入一种或多种辅助剂，或者在通过超压烧结进行的致密化情况下向粉末垫中加入一种或多种辅助剂，以进一步抑制不需要的反应。
17.权利要求16的方法，其中所述不需要的反应为分解和氧化。
18.权利要求16的方法，其特征在于，所述辅助剂是细小的金属粉末和/或易于分解的水合物。
19.权利要求1或2所述的方法，其中所述材料在致密化时的分解为汽化。
20.包含磷灰石的牙科或整形术用生物活性复合材料，所述复合材料包含有分解倾向的基团，其特征在于，所述复合材料是依据前述权利要求1-19中任一项的方法制得的。
21.权利要求20的生物活性复合材料，其中所述分解为汽化。
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| SE521938C2 (sv) | 2001-12-27 | 2003-12-23 | Cerbio Tech Ab | Keramiskt material, förfarande för framställning av keramiskt material och benimplantat, tandfyllnadsimplantat och biocement innefattande det keramiska materialet |
| JP5111761B2 (ja) * | 2003-12-18 | 2013-01-09 | イムノサイエンス株式会社 | チタン化合物の焼結体 |
| DE10360813A1 (de) * | 2003-12-23 | 2005-07-28 | Universität Hamburg | Hydroxylapatit-Metall-Verbundwerkstoff und ein Verfahren zu dessen Herstellung |
| JP4942136B2 (ja) * | 2005-07-11 | 2012-05-30 | 学校法人近畿大学 | 生体用材料を製造するための方法 |
| CN102910605B (zh) * | 2012-09-14 | 2014-06-04 | 陕西科技大学 | 一种含钛HA-ZrO2 生物复合纳米粉的制备方法 |
| CN102910604B (zh) * | 2012-09-14 | 2014-08-27 | 陕西科技大学 | 一种棒状含钛羟基磷灰石纳米晶的制备方法 |
| US9540286B2 (en) * | 2013-02-25 | 2017-01-10 | U.S. Department Of Energy | High pressure low temperature hot pressing method for producing a zirconium carbide ceramic |
| CN106495681A (zh) * | 2015-03-31 | 2017-03-15 | 蒋超 | 一种生物陶瓷 |
| CN105274416A (zh) * | 2015-09-30 | 2016-01-27 | 苏州蔻美新材料有限公司 | 一种磁性氧化锆生物陶瓷及其制备方法 |
| RU2652429C1 (ru) * | 2017-04-10 | 2018-04-26 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Биорезорбируемый материал и способ его получения |
| RU2760096C1 (ru) * | 2021-01-21 | 2021-11-22 | Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) | Способ получения низкотемпературного биорезорбируемого композиционного материала на основе гидроксиапатита, армированного частицами магния с помощью электроимпульсного метода компактирования для применения в качестве имплантата при остеосинтезе |
| CN114054742B (zh) * | 2021-11-10 | 2022-10-28 | 武汉理工大学 | 一种羟基磷灰石/金属钽/生物玻璃复合陶瓷材料及其制备方法和应用 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2827529C2 (de) * | 1978-06-23 | 1982-09-30 | Battelle-Institut E.V., 6000 Frankfurt | Implantierbarer Knochenersatzwerkstoff bestehend aus einem Metallkern und aus bioaktiven, gesinterten Calciumphosphat-Keramik-Partikeln und ein Verfahren zu seiner Herstellung |
| SE465571B (sv) * | 1989-04-10 | 1991-09-30 | Stiftelsen Ct Foer Dentaltekni | Saett att framstaella ett sammansatt keramiskt material med bioaktiva egenskaper |
| US5123844A (en) * | 1989-06-20 | 1992-06-23 | Agency Of Industrial Science And Technology | Living hard tissue replacement prepared by superplastic forming of a calcium phosphate base |
| JP2635415B2 (ja) * | 1989-07-21 | 1997-07-30 | 関西日本電気株式会社 | 含浸型陰極の製造方法 |
| FR2697243A1 (fr) * | 1992-10-26 | 1994-04-29 | Commissariat Energie Atomique | Procédé de préparation de pièces microporeuses en phosphate de calcium comprenant de l'hydroxylapatite, à microporosité contrôlée, et pièces obtenues par ce procédé. |
-
1998
- 1998-10-02 SE SE9803385A patent/SE513036C2/sv unknown
-
1999
- 1999-09-29 CA CA002345340A patent/CA2345340A1/en not_active Abandoned
- 1999-09-29 CN CNB998116149A patent/CN1146381C/zh not_active Expired - Fee Related
- 1999-09-29 DE DE69914781T patent/DE69914781T2/de not_active Expired - Fee Related
- 1999-09-29 AU AU13027/00A patent/AU761786B2/en not_active Ceased
- 1999-09-29 RU RU2001108384/15A patent/RU2227011C2/ru not_active IP Right Cessation
- 1999-09-29 BR BR9914233-3A patent/BR9914233A/pt not_active IP Right Cessation
- 1999-09-29 AT AT99956407T patent/ATE259207T1/de not_active IP Right Cessation
- 1999-09-29 KR KR1020017004209A patent/KR20010088836A/ko not_active Application Discontinuation
- 1999-09-29 US US09/806,455 patent/US6843943B1/en not_active Expired - Fee Related
- 1999-09-29 EP EP99956407A patent/EP1117366B1/en not_active Expired - Lifetime
- 1999-09-29 WO PCT/SE1999/001729 patent/WO2000019965A1/en not_active Application Discontinuation
- 1999-09-29 ES ES99956407T patent/ES2216589T3/es not_active Expired - Lifetime
- 1999-09-29 JP JP2000573327A patent/JP2002526389A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE69914781D1 (de) | 2004-03-18 |
| SE9803385L (sv) | 2000-04-03 |
| AU761786B2 (en) | 2003-06-12 |
| DE69914781T2 (de) | 2004-12-09 |
| EP1117366B1 (en) | 2004-02-11 |
| WO2000019965A1 (en) | 2000-04-13 |
| JP2002526389A (ja) | 2002-08-20 |
| ATE259207T1 (de) | 2004-02-15 |
| AU1302700A (en) | 2000-04-26 |
| RU2227011C2 (ru) | 2004-04-20 |
| SE9803385D0 (sv) | 1998-10-02 |
| KR20010088836A (ko) | 2001-09-28 |
| SE513036C2 (sv) | 2000-06-26 |
| ES2216589T3 (es) | 2004-10-16 |
| EP1117366A1 (en) | 2001-07-25 |
| US6843943B1 (en) | 2005-01-18 |
| CA2345340A1 (en) | 2000-04-13 |
| BR9914233A (pt) | 2001-06-19 |
| CN1321077A (zh) | 2001-11-07 |
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