CN1163142C - 控制释放活性物质的植物保护粒剂 - Google Patents
控制释放活性物质的植物保护粒剂 Download PDFInfo
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- CN1163142C CN1163142C CNB988082527A CN98808252A CN1163142C CN 1163142 C CN1163142 C CN 1163142C CN B988082527 A CNB988082527 A CN B988082527A CN 98808252 A CN98808252 A CN 98808252A CN 1163142 C CN1163142 C CN 1163142C
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- soil
- granulate
- shell
- plant protection
- protection products
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Abstract
本发明涉及植物保护粒剂，它以活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮为基础，且包含占粒剂重量0.1至50%的外壳，该外壳的至少按重量计50%由硫或含硫化合物组成。
Description
本发明涉及以活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮为基础的植物保护粒剂。
US-A 2,838,389描述了使用式(I)的四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮(通用名：棉隆)作为农业和园艺中的土壤消毒剂(decontaminant)。
对于将棉隆通过机械方式掺入土壤中的最终使用者而言，能够使用无尘粒剂是最大的优点。
制备这种基本上无尘的粒剂的方法描述于EP A 618 912中。在棉隆的制备过程中，将通式R1-NH-A-NHR(III)(R和R1独立地是氢或C1-C4-烷基，且A是1，2-亚乙基、1，3-亚丙基或1，4-亚丁基桥)的烷二胺，对结晶或颗粒进行控制，获得品质上对最终使用者有利的基本上无尘的棉隆粒剂。相应的产品有由BASF Aktiengesellschaft商品化生产的商标名为Basamid的产品。
森林生产杂志(Forest Prod.J.)43(2)：41-44(1993)，园艺学学报(Acta Horticulture)382(1995)p110等和《食品与纤维科学》，27(2)1995，pp183-197以及其中引述的参考文献描述了棉隆粒剂的使用和具有实际生物活性剂功用的缓释的产物异硫氰酸甲酯
CH3-N＝C＝S (II)
(MITC)的作用方式。因此，棉隆本身可以说只是作为前药物前体。
甚至是现在，对于在土壤中MITC由棉隆释放的方式与活化知之甚少。然而，由文献得知土壤pH、过渡金属或(例如)土壤湿度和土壤温度均起一定作用。这点已被我们的研究证实。
根据上面提到的EP 0 618 912制备的棉降粒剂虽然是基本上无尘的，但其对MITC释放的影响非常有限，因此不能够提供完全令人满意的方案来解决应用上的问题：控制活性物质释放和特别是延迟其释放。
业已发现，当将这样的棉隆粒剂使用在给定的高于30℃土壤温度和足够的土壤湿度下，MITC释放得特别快，当此粒剂掺入土壤，特别是在温室中施用时，在缺乏适当通风条件和不正确使用的情况下，MITC可以导致暂时的粘膜和眼睛刺激。
因此需要一种应用来充分延迟MITC的释放，使得负责施用该产品的人有足够的时间离开温室。
另一种土壤消毒剂气态甲基溴已知具有对臭氧有害的缺点。
安百亩(metam)流体和威百亩由于其非常快和强的挥发成气体的自然倾向，它们只能有限地使用于温室中，甚至例如在加尼福利亚，已经不许可使用。
《消耗臭氧层的物质的蒙特利尔公约》第四部分：评价甲基溴替代物的经济可行性，1997年4月报告第二卷在第260页提到棉隆作为甲基溴的潜在替代物，但指出了其未受训练的使用者施用的问题。
本发明的目的是提供一种以活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮为基础，其中活性物质被延迟和/或控制释放的植物保护粒剂。
我们发现，此目的通过以活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮为基础的植物保护粒剂而达到，该粒剂包含占粒剂总重量0.1至50wt％且其中至少50wt％为含硫化合物或硫本身组成的外壳。
从属权利要求和随后的描述揭示本发明的优选实施方案。
本发明还涉及用本发明粒剂以每公顷土壤表面1至1000kg的有效量处理土壤来防治线虫、土居昆虫、萌发的植物、土壤细菌和土壤真菌的方法。
本发明优选的是用EP 618 912描述的方法获得的棉隆粒剂，即，在制备时加入0.1至10mol％的二氨基亚烷基化合物R1NH-A-NHR(R、R1和A如开头所定义)的产品。至于进一步的细节，参见参考文献EP 618912。
外壳优选为粒剂的1至35，和特别是2至25wt％。
优选的是55至100，且特别优选的是，75至100wt％的壳由含硫化合物或元素硫组成。
特别优选的是壳材料是元素硫，特别是可以以含水分散液形式采用的那些产物。
因此，出人意外地发现，硫的含水分散液，如商品化的含水再分散浓缩物KumulusDF，特别适合于作为壳成分。
使用这些壳材料的优点是，它们可以通过流化床技术涂在棉隆颗粒上，而没有在加工过程出现的缺点，如附聚、形成粗颗粒或磨损方面的缺点。
这些硫分散液优选通过下述技术之一制备：
方法A：
采用水研磨技术用适宜的辅助剂由元素硫制备硫悬浮浓缩物
将硫元素如硫粉悬浮于水中，有利的是加入润湿剂和分散剂，且如果需要加入粘合剂。之后将仍就粗颗粒的硫悬浮液在普通或搅拌球磨中，用研磨介质例如玻璃研磨介质或其它矿物或金属研磨介质-具有通常为0.1-30毫米，优选0.6-2毫米的大小(平均直径)-磨碎成平均粒径优选小于10微米。
方法B：
由再分散于水中的熔融喷雾的硫颗粒制备硫悬浮浓缩物
熔融喷雾的硫颗粒如下获得：通过将元素硫如硫粉加热至高于120℃来熔融，并将所得的熔融体任选在加入润湿剂和分散剂之后在适宜的喷雾装置如喷雾塔中喷雾，通常是在冷却下，形成喷雾硫颗粒。
适合于此二技术的润湿剂和分散剂的实例是选自下列物质组的下列辅助剂：
脂肪酸聚氧乙烯酯，如月桂醇聚氧乙烯醚乙酸酯，
烷基聚氧乙烯或聚氧丙烯醚，如异十三烷基醇和脂肪醇聚氧乙烯醚，烷基芳基醇聚氧乙烯醚，如辛基酚-聚氧乙烯醚或三丁基酚聚氧乙烯醚，
乙氧化基的异辛基-、辛基-或壬基酚或蓖麻油、山梨醇酯，
芳基磺酸、烷基磺酸、烷基硫酸或其碱金属、碱土金属和铵盐，特别是芳基磺酸例如木素-、苯酚-、萘-和二丁基萘磺酸的盐，烷基磺酸、烷基芳磺酸、烷基硫酸、月桂基醚硫酸和脂肪醇硫酸的盐，脂肪酸、硫酸化的十六-、十七-和十八醇和脂肪醇乙二醇醚的盐，
磺化萘和其衍生物与甲醛的缩合物，
萘磺酸与苯酚和甲醛的缩合物，和
蛋白质水解物。
此外，木素亚硫酸盐废液和甲基纤维素同样是特别适合的。
可以在此提到的实例是：
苯磺酸与其C10-C16-烷基衍生物以及其钠、钾、钙和镁盐，二异丁基-、二异丙基-和二甲基萘磺酸及其相应的钠、钾、钙和镁盐、优选钠盐，乙氧基化十二烷醇与硫酸的单醚类、乙氧基化十二烷醇与硫酸的单醚类的铵和钠盐，十二烷基硫酸的各种盐(o、K、Ca、Mg)，十二烷基苯磺酸与钠、钾、钙、二乙醇胺或三乙胺的盐，萘磺酸与甲醛的缩合物的铵或钠盐，苯酚磺酸、尿素和甲醛的缩合物及其盐，二甲苯酰磺酸及其盐，和C12-C16-2-链烯磺酸的钠盐。
本发明粒剂优选在流化床装置中制备。为此，首先将棉隆粒剂进行流化，并在相同的时间，将通常含水的硫分散液(在这种分散液用作壳材料的情况下)、如果需要与其它的辅助剂如聚合物、润湿剂或分散剂、乳化剂或粘合剂一起喷雾到活性物质的颗粒上。
与硫分散液混合在一起或分别喷雾到棉隆颗粒上的适合的辅助剂和壳材料包括特别是下列粘合剂：
纤维素衍生物，如纤维素酯、纤维素醚、羧甲基纤维素、羟丙基甲基纤维素，水溶性胶如阿拉伯胶、黄蓍胶，藻酸盐，明胶，改性淀粉，如羧甲基淀粉钠，以及天然来源的辅助剂，和纤维素、乙酸纤维素、纤维素羧甲基醚及其钠盐，纤维素2-羟基丙基醚和纤维素2-羟基乙基醚，纤维素乙基醚和再生纤维素等等。
至少50wt％，优选55至100wt％的本发明粒剂的壳由硫或含硫化合物组成。为控制壳的性能，且特别是控制MITC的释放，除硫和含硫化合物之外，也可能使用例如占壳量最多达45wt％，优选至多40wt％的聚合物壳材料。
优选的是采用含水蜡分散液，它包含以含水蜡分散液计，5至40wt％的乙烯共聚物蜡，该蜡由10至25wt％的具有3至8个碳原子的α-烯属不饱和一-或二羧酸和90至75wt％的乙烯组成，其MFI值在190℃和2.16kp的负重下测定，为1至600，优选是5至500，和特别是15至300，或MFI值在160℃和325p下测定，为1至600，0.1至5wt％碱金属氢氧化物、氨、链烷醇胺或二烷醇胺和其混合物与余量的水(补至100％)。
特别适合于蜡分散液的乙烯共聚物含有10至25wt％，优选15至24wt％的具有3至8个碳原子的α-烯属不饱和一-或二羧酸，可以提到的实例是丙烯酸、甲基丙烯酸、巴豆酸、马来酸、富马酸和衣康酸。其中，优选的是甲基丙烯酸和特别是丙烯酸及其混合物。
该乙烯共聚物蜡的特征在于其MFI(熔体流动指数)或熔体指数。MFI指在一定的施加压力(负重)和某一温度下，可以被压过一定尺寸的喷嘴的聚合物的熔融体克数。熔体指数(MFI单位)根据下列标准确定：ASTM D 1238-65T，ISO R 1133-1696(E)或DIN 53 735(1970)。
除此之外，蜡分散液优选包含碱，通常是0.1-5，优选1至3wt％的碱金属氢氧化物，优选氢氧化钾或氢氧化钠，氨，在羟基烷基基团上各具有2至18个碳原子，优选是2至6个碳原子的单-、二-或三烷醇胺，或是所述烷醇胺的混合物或是在烷基和羟基烷基基团上各具有2至8个碳原子的二烷基单烷醇胺，或其混合物。胺的实例是二乙醇胺、三乙醇胺、2-氨基-2-甲基-1-丙醇或二甲基乙醇胺。优选使用氨。
由于在蜡分散液中的碱成分，此共聚物蜡中的羧基基团至少部分以盐形式存在。优选50至90％，特别是多达60至85％的这些基团是中和的形式。
特别优选的蜡分散液由下述成分组成或包含下述成分：5至40wt％乙烯共聚物蜡、0.1至5wt％氨和55至94.9wt％的水。上述乙烯共聚物蜡由75至90wt％乙烯单元和多达10至25wt％的具有3至8个碳原子的α-烯属不饱和一-或二元羧酸组成。
适合的聚合物壳材料的进一步的实例如下：
丙烯酸丁酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸和苯乙烯的共聚物，
丙烯酸丁酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸甲酯和苯乙烯的共聚物，
丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸和苯乙烯的共聚物，
丙烯酸丁酯、丙烯酸羟基乙酯和甲基丙烯酸甲酯的共聚物，
甲基丙烯酸丁酯、丙烯酸2-乙基己酯和苯乙烯的共聚物，
甲基丙烯酸丁酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸甲酯和苯乙烯的共聚物，
甲基丙烯酸正丁酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸甲酯和苯乙烯的共聚物，
乙烯-乙酸乙烯酯共聚物，
乙烯-丙烯酸共聚物的钠和铵盐，
甲基丙烯酸甲酯和丙烯酸、丙烯酸丁酯、甲基丙烯酸丁酯或其混合物的共聚物，
聚乙酸乙烯酯、聚乙烯醚、聚丙烯酰胺、聚酰胺、聚乙烯醇、聚乙烯吡咯烷酮、聚乙烯吡咯烷酮-乙酸乙烯酯共聚物，
乙酸乙烯酯与丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸或基混合物的共聚物，乙烯基吡咯烷酮与长链1-链烯的共聚物，巴豆酸、乙酸乙烯酯和丙酸乙烯酯的共聚物。
壳层还可以包含用于控制活性物质释放的物质。其实例有水溶性物质如聚乙二醇、聚乙烯吡咯烷酮和聚乙烯吡咯烷酮与聚乙酸乙烯酯的共聚物。其量是例如壳物质重量的0.1至5％，优选为0.1至3％。
上述壳聚合物是通常已知的或可以用已知方法获得(参见，例如，DE-A-34 20 168；EP-A 201 702；US-A 206 279)。
这些壳层任选通过溶液或分散液或所述壳物质与硫或含硫化合物在有机溶剂或水中的分散液喷雾涂敷。
优选的是使用具有聚合物含量尤其为0.1至50wt％，特别是1至35wt％的壳物质的含水悬浮液或乳液。在此情况下，还可以加入其它的辅助剂，以使加工最佳化，辅助剂例如为表面活性剂和固体物如滑石和/或硬脂酸镁。
上述描述的蜡分散液还可以用流化床技术，与硫分散液和/或其它辅助剂一起喷雾涂敷到棉隆颗粒上。
对于本发明提供的带有外壳的粒剂，与常规的商品化产品相比，特别是在高温下，MITC释放明显地延迟，却不会造成在处理后的衰变阶段的持续时间明显增加；换句话说，再播种前所需的MITC矿化作用在实际上与已知产品相同的时间段内进行。这是一种明显的技术优点。
本发明的植物保护粒剂还可以包括其它活性物质或可以与其它组合物合谐地一起、混合或依次分别施用。其它活性物质的比例优选是总重量的至多20wt％，特别是至多10wt％。适合的其它组合物对于本领域技术人员来说本身是已知的，且描述于文献中，因此，进一步的详情不再赘述。
实施例
实施例1：熔体喷雾硫颗粒的制备，并随后再分散于水中
将硫粉加热到高于120℃并熔融。将熔融体与作为润湿剂的木素磺酸钠和作为分散剂的二氧化硅混合。将此融熔体混合物在喷雾塔中使用双物质喷嘴喷雾。由此给出易于分散的喷雾颗粒(粒径：60＜x＜300微米)，含有0.3wt％的分散剂和大约20wt％的润湿剂。余下的为硫。之后获得的熔融体喷雾颗粒分散于等量水中，并将此分散液根据实施例3进一步加工。
实施例2：在搅拌磨中通过水-机械细研磨制备硫悬浮液
将硫粉悬浮于水中，加入木素磺酸钠作为分散剂。加入壬基酚聚乙氧基化物作为润湿剂。将此悬浮液调节成可用泵抽的浓缩物。优选的是50wt％的硫浓度。
为形成可喷雾的悬浮液，将此批料在实验室搅拌磨中研磨，直到获得40％＜2微米的颗粒分布。
以总的干质量计，硫的比例为80wt％，木素磺酸钠的浓度为19wt％，润湿剂的浓度为1wt％。加入消泡剂，如硅氧烷SRE至多达0.1％的浓度，以抑制在研磨过程中泡沫的形成。
实施例3：本发明棉隆粒剂的制备
将2千克根据EP 0 618 912制备的粒剂引入喷雾流化床。
之后用20分钟将50％硫含水悬浮液喷雾到这些载体颗粒上。在此期间，棉隆颗粒用130m3/h的空气量流化。硫含水悬浮液用1.5巴的压力喷雾。
下列样品用上面描述的方法制备：
表1
| 样品序号 | 外壳的重量比例及其组成 |
| 1 | 无壳(对照样品) |
| 2 | 如同实施例3的10％S颗粒 |
| 3 | 如同实施例3的20％S颗粒 |
| 4 | 如同实施例3的10％S颗粒+5％聚合物1 |
| 5 | 如同实施例3的5％S颗粒+5％聚合物2 |
在样品4中使用的聚合物1涉及根据EP 734,205的实施例1的蜡分散液；在样品5中使用的聚合物2是苯酚磺酸/甲醛/尿素缩合物的钠盐。
通过下列方法确定MITC的释放：
将400g干燥过和无块土壤(pH7.9 Limburgerhof site)与160mg样品1至5彻底混合，用50ml水润湿，并置于试验容器(玻璃，内径100mm，气体容积300ml)，之后密封，放置于气候控制室中。让10ml/分钟的纯化空气通过此容器。在离开此容器之后，此空气经加热的连接管直接通入气相色谱仪的火焰离子化检测器(FID)中。检测器信号实际上100％响应于测定气体的有机碳含量。除了异硫氰酸甲酯外，棉隆分解实际上通常没有其它FID可检则的化合物或挥发气体。使用校正气体(氮气中的丙烷)进行校正，考虑物质-特异性校正系数。
实验结果示于下文表2中。
表2
| 样品1 | 样品1 | 样品1 | 样品2 | 样品3 | 样品4 | 样品5 | |
| 测定时间(h) | MITC浓度(mg/m3) | MITC浓度(mg/m3) | MITC浓度(mg/m3) | MITC浓度(mg/m3) | MITC浓度(mg/m3) | MITC浓度(mg/m3) | MITC浓度(mg/m3) |
| 0.5 | 110 | 361 | 550 | 220 | 110 | 110 | 220 |
| 1 | 220 | 723 | 1210 | 660 | 440 | 165 | 770 |
| 2 | 303 | 1627 | 3080 | 1980 | 1870 | 440 | 2420 |
| 6 | 743 | 3795 | 8030 | 4620 | 5060 | 1705 | 5940 |
| 12 | 1320 | 4389 | 5280 | 3740 | 4070 | 2585 | 4620 |
| 18 | 1678 | 3589 | 3080 | 2640 | 2640 | 2585 | 2915 |
| 24 | 1859 | 2556 | 1760 | 1760 | 1650 | 2145 | 1815 |
| 温度(℃) | 15 | 25 | 35 | 35 | 35 | 35 | 35 |
进行的实验结果显示，在所有的情况下，在35℃下，包裹在壳中获得了明显延迟的MITC释放。释放速率大约相当于没有壳的粒剂在15℃下的释放速率。这点是优越的且是出人意外的，特别是在样品4的情况下，在掺入6小时后-这大约相应于实际中的应用-又获得高于在15℃下没有壳的粒剂的情况下获得的速率。这点是所需要的效果，因为由此获得了更快的MITC衰变速率，尽管最初延迟释放，且因此在新耕种的情况下，使更早的再播种成为可能。
其它积极效果是，在棉隆粒剂的施用量(优选在1至1000kg/ha的范围内，特别优选是10至800和尤其是100至600kg/ha土壤表面)下，有大量的硫加到土壤中，而硫是有肥效作用的，它对于植物生长有长期的良好作用。
而且，实际上硫还有杀真菌、杀线虫或杀虫作用。
Claims (6)
1.植物保护粒剂，它以活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮为基础，且包含占粒剂重量0.1至50％的外壳，按重量计，该外壳的至少50％由硫组成。
2.根据权利要求1的植物保护粒剂，其中悬浮浓缩物形式的硫作为外壳的原材料。
3.根据权利要求1或2的植物保护粒剂，其中包含的活性物质在添加0.1至10mol％式III二氨基亚烷基化合物的情况下制得，
R1-NH-A-NHR
其中，R和R1独立地是氢或C1-C4-烷基，且A是1，2-亚乙基、1，3-亚丙基或1，4-亚丁基桥。
4.一种防治线虫、土居昆虫、萌发的植物、土壤细菌和土壤真菌的方法，它包含用1至1000kg权利要求1至3之一的植物保护粒剂每公顷土壤表面的量处理土壤。
5.权利要求1至3之一的土壤保护粒剂作为土壤消毒剂的应用。
6.一种制备权利要求1至3之一的植物保护粒剂的方法，它包含将活性物质四氢-3，5-二甲基-1，3，5-噻二嗪-2-硫酮的颗粒通过流化床技术流化，并将之用壳材料的含水悬浮液涂敷。
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| DE19731528 | 1997-07-23 | ||
| DE19731528.3 | 1997-07-23 |
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| CN1163142C true CN1163142C (zh) | 2004-08-25 |
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| EP (1) | EP0998200B1 (zh) |
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| ITCT20000009A1 (it) * | 2000-04-20 | 2001-10-20 | Giuseppe Antonio Zanuccoli | Elemento inorganico bio-ossidabile, e/o suoi composti inorganici, e/oacidi inorganici con i quali combattere i nematodi del terreno, detti |
| DE10230801A1 (de) * | 2002-07-08 | 2004-02-05 | Basf Ag | Verfahren zur Vulkanisierung von Kautschuk oder Latex durch Applikation einer Mischung aus Schwefel und Komplexbildner |
| JP4518769B2 (ja) * | 2003-09-18 | 2010-08-04 | 日本曹達株式会社 | 多年生雑草の根絶方法 |
| JP4917322B2 (ja) * | 2005-02-18 | 2012-04-18 | シナノケンシ株式会社 | 電動機のクラッチ機構 |
| JP5220745B2 (ja) * | 2006-08-23 | 2013-06-26 | バイエル・クロップサイエンス・アーゲー | 農芸化学的活性物質の徐放のための新規製剤 |
| CN102084863B (zh) * | 2011-03-01 | 2012-03-28 | 宁波市鄞州浩斯瑞普生物科技有限公司 | 一种缓释的噻二嗪类物质的缓释制剂 |
| BR112013022141B1 (pt) * | 2011-03-10 | 2019-08-20 | Deepak Pranjivandas Shah | Composição agrícola compreendendo enxofre, zinco e ingrediente ativo pesticida |
| CN102870789B (zh) * | 2012-10-25 | 2014-01-15 | 联保作物科技有限公司 | 一种棉隆包膜控释颗粒剂 |
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| US2519891A (en) * | 1947-04-19 | 1950-08-22 | Dean | Sulfur coated diaphragm and method of making same |
| US2838389A (en) | 1952-09-03 | 1958-06-10 | Union Carbide Corp | Method of combatting weeds |
| GB973909A (en) * | 1962-04-30 | 1964-11-04 | Boots Pure Drug Co Ltd | Soil sterilant compositions |
| US4032319A (en) * | 1973-06-19 | 1977-06-28 | J. R. Simplot Company | Composite fertilizer and method for its manufacture |
| IL87986A0 (en) * | 1987-10-20 | 1989-06-30 | Exxon Chemical Patents Inc | Controlled release vegetation enhancement agents coated with sulfonated polymers,their production and their use |
| IL104081A (en) | 1991-12-21 | 1996-05-14 | Basf Ag | Preparation of de facto dust-free granules of tetrahydro - 3, 5 - dimethyl-1, 3, 5 - thiodiazine 2 - thion |
| US5454851A (en) * | 1993-02-26 | 1995-10-03 | Haifa Chemical South Ltd. | Slow release fertilizers |
| DE4317076A1 (de) * | 1993-05-21 | 1994-11-24 | Bayer Ag | Benzthiophencarbonsäureamid-S-oxide |
| JPH09502710A (ja) * | 1993-09-16 | 1997-03-18 | バイエル・アクチエンゲゼルシヤフト | ブテノール−トリアゾリル誘導体、それらの製造及び殺微生物剤としての利用 |
| DE4402034A1 (de) * | 1994-01-25 | 1995-07-27 | Bayer Ag | Halogenalkenyl-azolyl-Derivate |
| DE4411235A1 (de) * | 1994-03-31 | 1995-10-05 | Bayer Ag | Thiazolylpyrazolinone |
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| US6410042B1 (en) | 2002-06-25 |
| KR20010022141A (ko) | 2001-03-15 |
| EP0998200A1 (de) | 2000-05-10 |
| IL133998A (en) | 2004-02-08 |
| ZA986513B (en) | 2000-01-24 |
| IL133998A0 (en) | 2001-04-30 |
| AU8541698A (en) | 1999-02-16 |
| TR200000185T2 (tr) | 2000-05-22 |
| ES2189212T3 (es) | 2003-07-01 |
| AR016538A1 (es) | 2001-07-25 |
| JP4308422B2 (ja) | 2009-08-05 |
| AU748665B2 (en) | 2002-06-06 |
| EP0998200B1 (de) | 2002-12-18 |
| WO1999004634A1 (de) | 1999-02-04 |
| DE59806746D1 (de) | 2003-01-30 |
| HUP0002892A3 (en) | 2001-08-28 |
| HU224037B1 (hu) | 2005-05-30 |
| JP2001510775A (ja) | 2001-08-07 |
| HUP0002892A2 (hu) | 2000-12-28 |
| BR9811018A (pt) | 2000-09-26 |
| TW464473B (en) | 2001-11-21 |
| CN1267193A (zh) | 2000-09-20 |
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