CN1090684C - 带有锌或锌铝合金镀层的钢表面处理方法 - Google Patents
带有锌或锌铝合金镀层的钢表面处理方法 Download PDFInfo
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
Abstract
本发明涉及锌或锌铝合金的表面处理方法，该方法包括用pH＜3的包含由至少一种金属含氧离子与至少一种杂离子相结合而形成的配合物的水溶液，和与所选离子可相容的成膜耐酸树脂处理表面的步骤，金属含氧离子选自钼酸盐，钨酸盐和钒酸盐；杂离子选自P(V)、Al(III)、Si(IV)、Mn(II)、Mn(IV)、Zr(IV)、Ti(IV)、Sn(IV)、Ce(III)和Ni(II)。
Description
本发明涉及带有铝，锌或其合金，特别是铝/锌合金镀层的镀金属钢的抗蚀处理。
为了防止钢基体的生锈和腐蚀，广泛使用铝合金，例如55％(重量)的铝，余量基本上是锌(55Al/Zn)的合金作为钢的保护表面镀层。可是当这样的镀钢表面在贮存期间被安置在非常靠近的距离(例如象在钢板卷绕和叠合时所出现的那种情况)并长期受潮时，保护镀层本身就很容易受到腐蚀。根据镀层外观特征，对于主要只是镀锌的镀钢，这种腐蚀的残留物叫做白斑，对于镀层含有大量铝的镀钢，腐蚀残留物叫做黑斑。尽管镀钢的总使用寿命可能仍旧相同，但这些残留物往往会使这类镀钢失去销路。抗这种腐蚀的能力常称作湿堆积性能(wet stack performance)。
为了防止这种锈斑的形成，在运送给顾客之前，镀钢表面一般用含铬溶液进行处理，这种处理下文将叫做铬钝化。这种铬钝化提供了合理的防锈斑程度，但是铬溶液毒性剧烈。因此清除供这种钝化处理用的含铬残余物是困难的而且是昂贵的。
使用如美国专利4,385,940和4,264,378所叙述的磷酸盐和/或钼酸盐的非铬钝化体系也是已知的。可是这样的体系不能提供合适的湿堆识性能。
如美国专利3,053,962；3,053,693；3,630,791和4,637,840所描述的，在铬钝化表面施加树脂涂层和/或在树脂内加入铬，这也是已知的。与铬钝化自身的性能相比较，使用这种树脂能够增强镀铝，镀锌或镀其合金的钢的湿堆积性能，同时树脂还可以提供另一个优点，即在成形期间，例如成卷期间无需使用润滑油。正如最近的美国专利4,637,840所认识的，这是因为铝和铝合金镀层没有镀锌钢的自润滑特性。而且这样的润滑剂又增加了额外的成形操作费用，同时这样的润滑剂也会引起健康和安全方面的问题。
改进现有技术的上述的一种或几种缺点，正是本发明的目的。提供在通常的成形期间不需要使用润滑油，也不进行铬钝化，但是有满意的湿堆积性能的镀钢，这就是本发明优选实施方案的一个目的。
本发明的一个方面是涉及锌或锌铝合金的表面处理方法，该方法包括了用一种pH＜3，含有至少由一种金属含氧离子与至少一种杂离子相结合而形成的配合物的水溶液，和用一种与所选离子相容的成膜耐酸树脂处理所述表面的步骤。该金属含氧离子选自钼酸盐，钨酸盐和钒酸盐；杂离子选自磷(V)，铝(III)，硅(IV)，锰(II)，锰(IV)，锆(IV)，钛(IV)，锡(IV)，铈(III)和镍(II)。
本发明的第二方面是一分散体，此分散体包括：
在pH＜3的水性介质中，至少一种与至少一种杂离子相结合的金属含氧离子，金属含氧离子选自钼酸盐，钨酸盐和钒酸盐；杂离子选自磷(V)，铝(III)，硅(IV)，锰(II)，锰(IV)，锆(IV)，钛(IV)，锡(IV)，铈(III)和镍(II)，所述介质中已分散了相容的成膜耐酸树脂。
在本发明优选的实施方案中，树脂是一种非离子型表面活性剂稳定的悬浮液，更优选的是树脂是在至少一种具有不饱和作用反应性的不饱和脂肪醇烷氧化物存在下在水介质中由至少一种不饱和单体的聚合作用而衍生的。在特别优选的实施方案中，分散浴液中配合物金属与树脂的重量比小于0.5摩尔/千克干树脂固体。理想情况下，成膜树脂含有一种或多种耐酸交联剂，优选该耐酸交联剂是酸催化的。
在本发明进一步优选的实施方案中，水溶液中金属与树脂的比是每千克树脂固体0.005-0.5摩尔金属，优选0.05-0.6摩尔金属，更优选0.01-0.02摩尔金属。
在本发明进一步优选的实施方案中，配合物中金属含氧离子与杂离子之比是在1∶5-1∶12之间。
在本发明进一步优选的实施方案中，在pH＜2.5将含配合物的树脂水性分散体施用于表面。
钼作为含氧金属离子是优选的，而磷是优选的杂离子。
本发明现在将利用实例的方式进行更详细地说明。
应当按这样的方式选择适合于本发明的树脂，即在所使用的pH值条件下(最好pH＜2)贮存和施用期间能保持稳定，避免由于溶液中存在金属而引起不稳定。对酸稳定树脂可选自可溶的和水可分散的树脂，优选为与水溶液相结合。
这样的树脂典型情况下由不饱和单体，例如甲基丙烯酸甲酯；丙烯酸丁酯；丙烯酸乙酯；苯乙烯等，和不饱和官能单体，例如丙烯酸羟乙酯，丙烯酸，甲基丙烯酸等加到丙烯酸酯或共聚物的乳液中而制备的加聚物组成。
另外，优选的树脂含有空间稳定的乳液颗粒，这种颗粒是使用非离子表面活性剂而形成的，它耐低pH值，典型场合下耐小于2的pH值，并且仍是稳定的。合适的树脂本质上可以是热塑性的也可以是热固性的，或为了与其它树脂添加剂发生交联，优选树脂可以含有本技术领域所熟知的官能团。可是，尽管在这方面优选树脂应该是有反应性的，但是如果因为金属在溶液中的存在不能迅速发生交联，则这样的树脂是最合适的。
特别优选的树脂是国际专利申请PCT/AU 90/00565或美国专利4,504,618所叙述的聚合物颗粒的分散体。这些分散体使用了非离子表面活性剂的稳定剂，并发现这些分散体特别耐金属离子添加剂，在pH小于3，典型情况下小于2的酸性条件下仍然保持稳定。
优选地以干膜厚度小于3微米的膜来施用树脂。典型情况下，干膜厚度小于2微米。
通常使用钼酸盐，例如钼酸铵，钼酸钠或钼酸作为金属含氧离子物的来源，但是也可以使用其它的含有金属含氧离子的化合物。典型的情况下，钼酸盐是以0.02-0.12摩尔钼/千克树脂固体的浓度存在的，更优选地，是以0.03-0.06摩尔钼/千克树脂固体的浓度存在的。
如果金属浓度过大，则树脂膜的完整性遭到破坏，随后腐蚀保护作用降低。如果金属浓度太低，则处理将无效。
本发明使用的杂离子物可以以酸或盐的形式加到金属含氧离子的溶液中。优选情况下，使用磷酸作为磷的来源，使用氯化铝作为铝的来源，硅酸钠是硅的最佳来源，而四氯化锆是锆的最佳来源。
优选地，将铝蚀剂加到溶液中，例如氟化钠溶液或四氟硼酸钠溶液，但是也可以应用其他的铝蚀剂。本发明典型情况下使用0-0.012摩尔氟化物/千克树脂固体颗粒。更优选地是0.004-0.008摩尔氟化物/千克树脂固体颗粒。最佳条件下，应选择与氟化物可相容的树脂，因此氟化物仍能加到乳胶液中，并可从一单浴液中施涂。
已经发现，根据本发明处理的抗蚀特性在pH＞5时变得无效，因此根据本发明的酸化树脂分散体的pH优选地在pH 1-pH 3之间，更优选地pH＜2。根据本发明的分散体优选地通过加入酸而进行酸化，所加入的酸既可以是有机酸也可以是无机酸，例如磷酸。
在施用期间浴液通常是在室温下。
在根据本发明的杂离子存在下使溶液中的钼酸盐或钨酸盐酸化时，形成了杂多酸配合物。根据所使用的杂离子不同，杂离子与钼或钨的比是在改变的。例如，当杂离子是磷时，磷钼比典型情况下1∶12-1∶6。当杂离子是铝时，铝钼比或铝钨比是1∶5-1∶7，典型情况下1∶6，而当杂离子是硅时，此比值是1∶10-1∶14，典型情况下是1∶12。
在根据本发明的优选浴液组合物中，使用钼作为含氧离子部分，钼在浴液中以0.005-0.5摩尔钼/千克树脂固体比(也就是0.05％-5％干树脂重量为基)存在。优选地0.05-0.06，更优选地0.01-0.02摩尔钼/千克树脂固体颗粒。
耐酸乳液典型情况下在施用浴液中是以约50％的固体颗粒提供的，但通常以25％-35％的固体颗粒提供的。
在本发明优选的实施方案中，耐酸交联剂是以树脂分散体的形式加入的。这种树脂分散体例如可以是咪唑酮树脂或磷化环氧树脂等，或它们的组合。应当这样来选择交联剂，要使它们在所使用的pH条件下是稳定的。能耐溶液中存在的金属离子。如果在树脂组合物中加入交联剂树脂，可以使用交联剂树脂固体颗粒占总树脂固体颗粒重量直到15％。例如如果使用咪唑酮系的糖代联脲(glycouril)甲醛树脂作为交联树脂，如果选择合适的官能团，那么5-8％的树脂固体颗粒可以是交联树脂。如果应用磷化环氧树脂基交联剂，那么可以应用含量2％-10％，优选地3％-6％(以总树脂固物为基)。
可以这样地用分散体，方法是将基体浸入浴液中，利用辊镀机任何其它合适的施用手段。
作为例示根据下面例1-例5所示的方法制备供本发明使用的各种耐酸树脂。如果不另作说明，组合物是按重量份数表示的。例1
制备了一种耐酸树脂其单体组成为691份甲基丙烯酸甲酯、342份丙烯酸正-丁酯、57份丙烯酸羟乙酯、23份甲基丙烯酸、23份丙氧基三丙烯酸甘油酯，和115份非离子表面活性剂。表面活性剂是依照类似于国际专利申请PCT/AU 90/00565的例2的方法制备的，但含有约1摩尔的不饱和链和23摩尔的环氧乙烷。
树脂依照类似于国际专利申请PCT/AU 90/00565的例5所述的方法作为水分散体制备的，和含有44.4％非挥发固体。例2
耐酸树脂乳液是按照美国专利4,504,618的例13的方法制备的，其单体组成为甲基丙烯酸甲酯17.8份、丙烯酸正丁酯9.8份、丙烯酸0.9份，和使用了美国专利4,504,618的例13所述的非离子表面活性剂1.5份。乳液具有29.0％非挥发固体。例3
根据国际专利申请PCT/AU 90/00565的例3制备了耐酸树脂，该树脂的单体组成为甲基丙烯酸甲酯276.28份、丙烯酸丁酯136.90份、丙烯酸羟乙酯22.70份、甲基丙烯酸9.08份、丙氧基三丙烯酸甘油酯9.08份，45.94份非离子表面活性剂。表面活性剂含有约1摩尔不饱和链和40摩尔环氧乙烷。
树脂按照上述例1作为水分散体制备的，含有49.2％非挥发固体。例4
制备耐酸树脂水分散体，其单体成为甲基丙烯酸甲酯166.2份、丙烯酸丁酯123.4份、苯乙烯81.6份、丙烯酸羟乙酯20.4份、甲基丙烯酸8.16份、丙氧基三丙烯酸甘油酯8.16份和41.3份上例1所述非离子表面活性剂，该分散体含有44.5％非挥发固体。例5
采用PCT/AU 90/00565例5的方法制备耐酸树脂水分散体，其单体组成为甲基丙烯酸甲酯288.25份、丙烯酸丁酯148.03份、丙烯酸羟乙酯8.72份、丙烯酸8.72份、丙氧基三丙烯酸甘油酯8.72份，和47.55份如例3所述的非离子表面活性剂。树脂分散体含有48.8％非挥发固体。例6
将0.543克的钼(以(NH4)6Mo7O24·4H2O的形式)和0.014克的氟化物(以NaF的形式)加到根据例1的耐酸树脂水分散体中(100克树脂固体)以制备根据本发明的镀层组合物。然后用磷酸(85％)调节pH到2。例7
表1列出了用根据本发明的水性组合物复镀55Al/Zn镀钢和加入将按上述例1-例5制备的各种耐酸树脂的结果。如表1所示，所处理的组合物含有钼酸铵四水化合物和各种数量的可从Eastman Chemicals International Ltd买到的Texanol(2，2，4-三甲基乙基戊烷-1，3-二醇单异丁酸酯，一种聚结剂)，可从Cytec Australia买到的Cymel 1175交联树脂和磷化环氧树脂。用磷酸(85％)调节pH到1.5。向基体施加镀层，为了达到镀金属钢100℃的最高温度，镀层加热25秒钟，得到约2-3微米厚度的膜。
8星期后在40℃时测量湿贮存斑点(表面，剥离和锈斑)，和4星期70℃测量湿贮存斑点，表1列出了测量结果。
表1使用的湿贮存等级是根据下列内容来评定的。湿贮存等级
| 表面 | 混浊膜(blushing) |
| 10 无变化8 微小变化6 浅淡灰色4 淡灰色2 深灰色0 黑色 | 10 没有8 不透明6 斑点＜30％4 30-50％表面2 ＞50％表面0 整个表面 |
| 剥离 |
| 10 没有8 小点-徽小/分散的(＜50％表面)8 微小的1-3毫米直径(＜20％表面)7 分散的1-3毫米(＜12％表面)6 微小的＞3毫米直径(＜20％表面)4 全部表面，＞3毫米直径3 ＜30％脱落2 1/2膜脱落0 膜脱落 |
| 锈斑 |
| 10 无9 微小的(＜1毫米)，分散的(不连续的)8 1-2毫米，≤2边(≤2 sides)7 1-2毫米达到四边(up to 4 sides)6 1-3毫米达到四边5 ＞3毫米达到四边4 四周蠕变(creep aroumd edges)3 表面上锈斑＜30％2 表面上锈斑＜60％0 整个表面。 |
根据National Coil Coaters Association在1980年5月出版的TechnicalBulletin No.II-17的内容测定了有机镀层的抗粘着性。
树脂是根据上述例1作为水分散体制备的，涂有本发明组合物的基体显示出卓越的抗蚀性和长期的防止黑锈斑的作用，也显示出油漆的良好粘附性。
虽然本发明是依据特例进行说明的，但是本领域技术人员将会懂得本发明可以以许多其它的方式来进行实施。
表 1
(A)交联体固体克数/100克乳液树脂固体这些例子中使用了Cymel 1175。(B)磷化环氧固体克数/100克乳液树脂固体。(C)100克乳液树脂固体克数。(D)1克加到混合物中的钼酸铵四水合物[(NH4)6Mo7O24·4H2O](以钼酸盐/氟化物/酸溶液存在)/100克乳液树脂固体。
| 树脂 | (A)交联树脂 | (B)磷化环氧树脂 | (C)TEXANOL | (D)钼酸铵四水合物 | pH | 湿贮存斑点 | 结块 | 混浊膜 | ||
| 表面40 70 | 剥离40 70 | 锈斑40 70 | ||||||||
| 例1例1例1 | 5.55-- | --- | 11.1011.3710.56 | 1.001.00- | 1.51.51.5 | 9 8- 8- 2 | 10 5- 5- 3 | 8 3- 3- 7 | 99- | 10010 |
| 例2 | - | - | - | 1.00 | 1.5 | 8 - | 10 - | 3 - | 9 | 10 |
| 例3例3 | 6.066.03 | -5.35 | 4.064.39 | 1.001.00 | 1.51.5 | 9 69 6 | 9 1010 10 | 8 37 8 | -9 | 1010 |
| 例4例4例4例4 | --5.786.30 | ---3.25 | 4.814.814.514.68 | -1.001.001.00 | 1.51.51.51.5 | 0 -8 08 8- 9 | 4 -10 -10 9- 10 | 0 -3 -7 7- 7 | --8- | 1061010 |
| 例5例5例5 | 7.387.56- | -5.115.11 | 4.134.964.96 | 1.001.00- | 1.51.5- | 10 8- 8- 10 | 10 10- 10- 3 | 8 3- 5- 8 | 88- | 10910 |
Claims (20)
1.带有锌或锌铝合金镀层的钢表面处理方法，该方法包括用pH＜3和含有至少由一种金属含氧离子与至少一种杂离子相结合而形成的配合物的水溶液和与所选离子相容的耐酸成膜树脂处理所述表面的步骤，金属含氧离子选自钼酸盐、钨酸盐和钒酸盐；杂离子选自磷(V)、铝(III)、硅(IV)、锰(II)、锰(IV)、铈(III)、锡(IV)和镍(II)，其中利用非离子表面活性剂使树脂稳定在悬浮液中。
2.根据权利要求1的方法，其中树脂含有一种或多种丙烯酸酯。
3.根据权利要求2方法，其中树脂包括一种或多种选自甲基丙烯酸甲酯、丙烯酸n-丁酯、丙烯酸羟乙酯，和丙氧基三丙烯酸甘油酯之类的丙烯酸酯。
4.根据上述权利要求的任一方法，其中树脂是在至少一种具有不饱和作用反应性的不饱和脂肪醇烷氧化物存在下在水介质中由至少一种不饱和单体的聚合作用而衍生的。
5.根据上述权利要求的任一方法，其中树脂还包括耐酸交联剂。
6.根据权利要求5的方法，其中耐酸交联剂是酸催化的。
7.根据上述权利要求的任一方法，其中施加树脂使成为干膜厚度小于3微米的膜。
8.根据权利要求7的方法，其中干膜厚度小于2微米。
9.根据上述权利要求的任一方法，其中金属含氧离子是钼酸盐。
10.根据上述权利要求的任一方法，其中杂离子是磷。
11.根据上述权利要求任的一方法，其中水溶液中金属与树脂的比是每千克树脂固体0.005-0.5摩尔金属。
12.根据权利要求11的方法，其中金属与树脂的比是每千克树脂固体0.05-0.6摩尔金属。
13.根据权利要求12的方法，其中金属与树脂的比是每千克树脂固体0.01-0.02摩尔金属。
14.根据上述权利要求的任一方法，其中配合物中金属含氧离子与杂离子之比是在1∶5-1∶12之间。
15.根据上述权利要求的任一方法，其中溶液还包括至少一种含氟化物的化合物。
16.根据上述权利要求的任一方法，其中在pH＜2.5将含配合物的树脂水性分散体施用于表面。
17.根据上述权利要求的任一方法，其中表面是55Al/Zn镀层。
18.用上述任一权利要求的方法处理的镀金属钢。
19.用于上述任一权利要求的方法的分散体，该分散体包括：
在pH＜3的水性介质中至少一种与至少一种杂离子相结合的金属含氧离子，金属含氧离子选自钼酸盐、钨酸盐和钒酸盐，杂离子选自磷(V)、铝(III)、硅(IV)、锰(II)、锰(IV)、锆(IV)、钛(IV)、锡(IV)、铈(III)和镍(II)，所述介质中使用非离子表面活性剂已分散了相容的成膜耐酸树脂。
20.根据权利要求19的分散体，还含有耐酸交联剂。
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| DE19923118A1 (de) | 1999-05-19 | 2000-11-23 | Henkel Kgaa | Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren |
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1994
- 1994-11-11 BR BR9408073A patent/BR9408073A/pt not_active IP Right Cessation
- 1994-11-11 CN CN94194788A patent/CN1090684C/zh not_active Expired - Fee Related
- 1994-11-11 US US08/640,860 patent/US5985047A/en not_active Expired - Fee Related
- 1994-11-11 ES ES95900557T patent/ES2148468T3/es not_active Expired - Lifetime
- 1994-11-11 WO PCT/AU1994/000695 patent/WO1995014117A1/en active IP Right Grant
- 1994-11-11 DE DE69424066T patent/DE69424066T2/de not_active Expired - Fee Related
- 1994-11-11 CA CA002176332A patent/CA2176332C/en not_active Expired - Fee Related
- 1994-11-11 AT AT95900557T patent/ATE191937T1/de not_active IP Right Cessation
- 1994-11-11 AU AU81350/94A patent/AU678075B2/en not_active Ceased
- 1994-11-11 JP JP51410395A patent/JP3618101B2/ja not_active Expired - Fee Related
- 1994-11-11 NZ NZ276028A patent/NZ276028A/en not_active IP Right Cessation
- 1994-11-11 EP EP95900557A patent/EP0730673B1/en not_active Expired - Lifetime
- 1994-11-14 MY MYPI94003033A patent/MY111662A/en unknown
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1999
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| US3528860A (en) * | 1967-10-04 | 1970-09-15 | Oakite Prod Inc | Surface coating compositions and their use |
| JPS60240773A (ja) * | 1984-05-14 | 1985-11-29 | Kobe Steel Ltd | 耐食性の優れた表面処理鋼材 |
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| AU5223793A (en) * | 1993-01-05 | 1994-07-14 | Chemetall Corp. | Method and composition for treatment of metals |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69424066T2 (de) | 2001-01-11 |
| EP0730673A1 (en) | 1996-09-11 |
| CA2176332C (en) | 2005-05-03 |
| AU8135094A (en) | 1995-06-06 |
| BR9408073A (pt) | 1997-08-12 |
| MY111662A (en) | 2000-10-31 |
| JPH09505111A (ja) | 1997-05-20 |
| ES2148468T3 (es) | 2000-10-16 |
| JP3618101B2 (ja) | 2005-02-09 |
| CA2176332A1 (en) | 1995-05-26 |
| WO1995014117A1 (en) | 1995-05-26 |
| CN1141064A (zh) | 1997-01-22 |
| ATE191937T1 (de) | 2000-05-15 |
| DE69424066D1 (de) | 2000-05-25 |
| US6287394B1 (en) | 2001-09-11 |
| EP0730673B1 (en) | 2000-04-19 |
| NZ276028A (en) | 1997-03-24 |
| EP0730673A4 (en) | 1998-01-07 |
| US5985047A (en) | 1999-11-16 |
| AU678075B2 (en) | 1997-05-15 |
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