CN100371089C - 镀银电路的改良涂层 - Google Patents
镀银电路的改良涂层 Download PDFInfo
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Classifications
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/07—Electric details
- H05K2201/0753—Insulation
- H05K2201/0769—Anti metal-migration, e.g. avoiding tin whisker growth
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
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- Organic Chemistry (AREA)
- Chemically Coating (AREA)
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Abstract
本发明公开了一种提高金属表面可焊性的方法,其中该金属表面在焊接前以浸渍或化学银镀层来镀敷,此后浸渍银镀层用碱性聚合物涂料处理,该碱性聚合物涂料包含水性乙烯基聚合物、水性丙烯酸聚合物、抗菌剂和苯并三唑或苯并咪唑化合物,以产生耐电迁移的沉积物,该沉积物在表面上提供防锈及防蚀涂层。
Description
技术领域
本发明一般性地涉及一种用溶液处理表面的方法,该溶液可提高表面的可焊性,更重要的是该溶液可作为该表面的防锈或防蚀剂。该方法可特别用于印刷电路板的制造和装配。
背景技术
焊接通常用来对多种物体进行机械、机电或电气连接。因为每种应用对表面制备都具有其自身的特定需求,因此接合处的预期功能间的差别很重要。在三种焊接应用中,进行电气连接是要求最高的。
在应用印刷电路的电子设备制造中,可通过将元件的导线焊接至通孔、焊垫、焊盘及其它连接点(全部称为“连接区域”)而得到电子元件与印刷电路的连接。典型地,连接可利用波焊技术来进行。
为了使该焊接操作容易,印刷电路制造者需要将通孔、焊垫、焊盘及其它连接点布置成可接受随后的焊接工艺。因此,这些表面必须可容易地由焊料润湿,并允许与电子组件的导线或表面进行整体的导电连接。因为这些需求,印刷电路制造者已设计出多种可保持和提高表面可焊性的方法。
所讨论的解决表面良好可焊性的一种方法为对该表面提供焊料预涂层。这典型地可通过称为热空气焊接整平法的方法或通过某些形式的镀敷方法来完成。但是,在印刷电路的制造中,该方法具有一些缺点。使用热空气焊接整平法会导致无法接受的高比率的因短路而造成的缺陷,特别是当处理小型电路时。如果使用镀敷,因为不容易有选择地对这些区域提供焊料,故必须对该板的全部导电区域镀敷焊料,这会对随后焊接掩模的涂敷产生严重的问题。此外,前述方法效率低且相对昂贵。
另一种解决这些表面良好可焊性的方法为对该表面镀敷上贵金属(如金、钯或铑)的精整加工(final finish)涂料。Bengston等人的美国第5,235,139号专利(其教示以参考方式并于本文)提出一种实现该贵金属精整加工的方法。Bengston等人建议通过化学镀敷将镍-硼镀敷到欲焊接的铜区域中,接着镀敷贵金属涂料(如金)。还可参见Juskey,Jr.等人的美国第4,940,181号专利(其教示以参考方式并于本文),其教示了类似的方法,先化学镀铜,接着是电解铜,接着是镍,接着是金,从而作为可焊表面。这些工艺良好,但是耗时且昂贵。
已进行多种尝试以将焊料有选择地涂敷到仅仅所需要的区域。这些方法之一描述于Durnwith等人的美国第4,978,423号专利中(其教示于此以参考方式并入本文),其包括在焊接镀敷的连接区域上使用有机抗蚀剂,接着在涂敷焊接掩模前从铜线路上有选择地剥离锡-铅。其它已知的有选择焊接法还可参见Larson的美国第5,160,579号专利,其教示以参考方式并入本文。
直接焊接至铜表面是困难且不相容的。这些问题主要是由于无法在整个焊接操作中保持铜表面清洁及无氧化。已发展出多种有机处理方法以将铜表面保持在容易焊接的状态。例如,参见Kinoshita的美国第5,173,130号专利,其教导使用特定的2-烷基苯并咪唑作为铜的预熔剂,以保持铜表面的可焊性。已证明Kinoshita所教导的处理方法是成功的,但是仍然需要改善该工艺的可靠性。
本文所建议的保持可焊性的方法是在焊接前在欲焊接的铜表面上浸渍或化学镀敷银镀层。但是,已发现当使用前述方法时,当于湿气存在下使用该电路(即有电压电势存在)时,该银涂层趋向于通过电迁移机理发展出分枝或细线。
发生电迁移的趋势可使用Bellcore GR-78-CORE(13.2.5,13.2.7)标准测试程序(其全部以参考方式并于本文)中详细指明的标准技术来测量。前述的Bellcore程序可测量在电路部件间的平均绝缘电阻。Bellcore及IPC标准要求该平均绝缘电阻在初值(其在85℃/85%相对湿度、无偏压处理96小时后获得)与终值(其在85℃/85%相对湿度、施加10V直流偏压处理附加的500小时后获得)间的减少不超过十分之一。
解决银镀层电迁移的一种方法是在该银镀层上涂布另一种更惰性的金属(如金)。该方法的缺点为金镀层的费用和需要其它工艺步骤。
解决浸渍银镀层电迁移的另一种方法描述于Kukanskis的美国第6,444,109号专利中,其教示于此以参考方式并入本文。在该方法中,用选自于由下述物质组成的组中的添加剂来处理浸渍银镀层:脂肪胺、脂肪酰胺、季盐、两性盐、树脂胺、树脂酰胺、脂肪酸、树脂酸、前述任何物质的乙氧基化衍生物,及前述任何物质的混合物。
本发明的目的是建议一种保持并提高铜表面可焊性的方法,该方法通过用新颖的银镀层(其比现有技术的银沉积物更耐电迁移)镀敷铜表面。本发明的进一步目的是通过将聚合物溶液加入到银镀浴或通过使用聚合物溶液作为后浸渍处理,增加银镀层的耐迁移性,并为银镀层提供防锈或防腐蚀性。
发明内容
本发明提出使用浸渍或化学镀银涂层,作为多种表面(特别是铜表面)的改进的可焊性保持剂。本发明还公开了用来沉积该浸渍银涂层的优选组合物。该新颖的镀银方法产生银镀层,其比常规的银沉积物更耐电迁移。所建议的方法对于有效保持表面(特别是印刷电路板上的铜表面和连接区域)的可焊性是一种通用的、低成本的方法。
此外,本发明通过在镀银表面上使用聚合物溶液进行后浸渍处理,可增加银镀层材料的耐迁移性和抗锈或抗腐蚀性。
具体实施方式
本发明提出一种保持并提高金属表面(特别是铜表面)的可焊性的方法。所建议的方法包含下列步骤:
a)清洁金属表面;
b)非强制选择地,蚀刻该金属表面;
c)用镀银溶液处理该金属表面,所述镀银溶液包含:
1.可溶的银离子源;
2.酸;
3.非强制选择的添加剂,选自于由下述物质组成的组:脂肪胺、脂肪酰胺、季盐、两性盐、树脂胺、树脂酰胺、脂肪酸、树脂酸,和前述物质的混合物;
4.非强制选择的咪唑、苯并咪唑或咪唑衍生物或三唑衍生物;
5.非强制选择的氧化剂;以及
d)用溶液处理该浸渍镀银表面,所述溶液包含选自于由水性乙烯基聚合物或共聚物、水性丙烯酸聚合物或共聚物和前述物质的混合物组成的组中的材料,和非强制选择的选自于由三唑、咪唑和它们的衍生物组成的组中的化合物。
已发现浸渍或化学镀敷银沉积物提供优良的可焊性保持剂,其在印刷电路板的制造中特别有用。已意外发现在印刷电路应用中以单纯的或化学镀敷浸渍银沉积物达到的可焊性超过由现有技术的镍-金镀敷工艺(如描述于美国第5,235,139号专利)所达到的可焊性;且前述的可焊性意外地超过由其它浸渍沉积物达到的可焊性。从下述实施例中可看出,本发明的方法可在不利条件下产生极度可焊的表面。在印刷电路应用中,该表面对于金属线是可粘结的。
浸渍镀敷是由置换反应产生的一种方法,通过置换反应,被镀敷的表面溶解于溶液,同时被镀敷的金属从镀敷溶液中沉积到表面上。浸渍镀敷不需事先的表面活化就可开始。欲镀敷的金属通常比表面金属更加惰性。因此,浸渍镀敷通常明显较易控制且明显比化学镀敷(其在镀敷前需要复杂的自动催化镀敷溶液和活化表面的工艺)更节省成本。化学镀敷如名称所暗示为这样一种镀敷方法,其通常使用化学还原剂将被镀敷金属从溶液中还原到欲镀敷的表面上。根据被镀敷金属的性质和欲镀敷的表面,可能需要使用催化剂来活化表面。
可溶的银离子源可来自多种银化合物。已发现硝酸银是最优选的。银在镀敷溶液中的浓度范围为每升0.1~25克,但最优选以每升0.5~2克的浓度存在。
虽然多种酸都适合用于该配方中,甲磺酸或硝酸是最优选的。酸在镀敷溶液中的浓度范围为每升1~150克,但优选的范围为每升5~50克。
包含在镀银溶液中的咪唑通常在镀敷溶液中提供明显的优点,但是在浸渍或化学镀银中特别有用且优良。发明人已发现,产生自包含咪唑的镀浴的银沉积物与从不含咪唑的浴中所镀敷的银沉积物相比更亮、更平滑且更具有粘性。此外,含有咪唑的镀浴与同等的不含咪唑的镀浴相比具有更长的有效寿命。可使用的合适的咪唑及咪唑衍生物的例子论述于美国第6,444,109号专利中。
非强制选择地,镀敷溶液还可有利地包含氧化剂。就这一点而言,硝基芳香族化合物,更优选二硝基化合物,如3,5-二硝基羟基苯甲酸是优选的。该氧化剂在溶液中的浓度范围为每升0.1~25克,但优选为每升0.5~2克。
非强制选择地,可使用选自于由脂肪胺、脂肪酸、脂肪酰胺、季盐、两性盐、树脂胺、树脂酰胺、树脂酸及前述物质的混合物组成的组中的添加剂,来进一步防止或明显降低银镀层电迁移的趋势。合适的添加剂的例子论述于美国第6,444,109号专利中。如果使用,前述添加剂在浸渍银镀浴中的浓度范围为每升0.1~15克,但优选为每升1~5克。在镀浴本身中掺入添加剂是优选的方法。
为了防止或明显降低浸渍银镀层电迁移的趋势并提供防锈及防腐蚀性,发明人已发现在镀敷沉积物上提供聚合物溶液可提供有益的结果。该聚合物溶液通常包含一种或多种水性乙烯基聚合物或共聚物、和/或一种或多种水性丙烯酸聚合物或共聚物、和优选的抗菌剂及三唑或咪唑型化合物。优选在随后的处理步骤中涂敷该聚合物涂布溶液。
合适的水性乙烯基聚合物包括UCAR乙烯基树脂分散体,如可从Union Carbide-Dow购得的UCARAw-875。另一种合适的水性乙烯基共聚物可以DP6-4586TM的商品名从Allied Colloids Limited购得。在聚合物溶液中,水性乙烯基聚合物或共聚物通常以20~50重量%的量存在,但优选以30~45重量%的量存在。乙烯基聚合物或共聚物的Tg优选为40~100℃,分子量为2,000~50,000,酸值为45~100且pH为7~9。
合适的水性丙烯酸聚合物包括可从Johnson Chemicals购得的Joncryl142和可从Morton Chemicals购得的MONCRYL350。其它合适的水性丙烯酸共聚物可以GlascolTM H及P的商品名从AlliedColloids Limited购得。在聚合物溶液中,水性丙烯酸聚合物通常以5~30重量%的量存在,但优选以30~45重量%的量存在。丙烯酸聚合物或共聚物的Tg优选为0~80℃,分子量为1,000~50,000且pH为7~9。
优选使用抗菌剂,且其优选为异噻唑或1,2-噻唑。一种合适的抗菌剂可以MergalK7的商品名从Riedel-de Haen购得。另一种合适的抗菌剂为FUNGITROL158,其可从International Specialty ProductsCompany购得。在聚合物溶液中,抗菌剂通常以0.5~2重量%的量存在。
在本发明中优选使用的三唑或咪唑型化合物包括苯并三唑、苯并咪唑、咪唑和组氨酸。在含聚合物的溶液中,该化合物通常以0.5~5重量%的量,更优选以0.5~2重量%的量存在。
聚合物溶液优选还可含氨或其它碱,以将该溶液的pH调整至大约7~11,优选为9~10。
浸渍镀银溶液可在本发明的方法中从室温至200的温度范围内使用,但优选在80~120使用。镀敷溶液中的浸渍时间范围为1~30分钟,但优选为1~5分钟。
使用浸渍或化学镀银溶液以在欲焊接的表面上镀敷一薄层的银。相信所产生的银涂层厚度应该为1~100微英寸,优选的厚度为10~60微英寸,以有效提高并保持表面的可焊性。虽然该方法在多种表面的焊接中均有效,其在铜表面(如印刷电路板上的连接区域)的焊接中特别有用。
在使用本发明的浸渍或化学镀银技术将材料镀敷后,将材料浸入聚合物溶液中至少15秒,且可长至数分钟。该材料可使用如晾干、烘烤或吹风等技术来干燥。优选在室温及pH为8.5~10.5的条件下操作聚合物溶液。
虽然此技术可有利地使用在几乎任何表面上,其在印刷电路板,特别是在裸铜覆焊接掩模(SMOBC)板的制造中特别有用。因此,在SMOBC板的制造中,将焊接掩模覆盖至板表面,然后曝光及显影以显露出连接区域。这些连接区域基本上为在板上仅曝露出铜的区域,其余部分基本上被焊接掩模所覆盖。在利用焊接的大部分情形中,当在后续的制造操作中电子组件将被放置在板上时,这些曝露的连接区域因此被指定为附着点。因此,必须提高并保持这些曝露点(通常为铜)的可焊性。
优选使用酸清洁剂来清洁这些区域,随后微蚀刻以制备可接受浸渍镀敷的表面。在该优选的制备之后,将板浸入浸渍镀银溶液中,由此可获得适当厚度的银沉积物。随后,将板浸入本发明的碱性聚合物涂布溶液中。
本发明仅以下列实施例来进一步描述说明,这些实施例并不以任何方式限制发明自身。在每个实施例中,使用标准IPC-B-25测试电路板来提供一致性。IPC-B-25标准全文以参考方式并于本文。
实施例1
以如下方式制备本发明的聚合物涂布溶液:
1.将DP6-4586TM(可从Allied Colloids Limited购得)加入至槽中,并开始搅拌;
2.在搅拌下将GLASCOL(可从Allied Colloids购得)加入至该槽;
3.在搅拌下将MergalTM(可从Riedel-de Haen购得)溶液加入至该槽;
4.在搅拌下将IrgametTM(可从Ciba-Geigy购得)加入至该槽;
5.将氨加入至该槽至pH9~10,且搅拌该混合物至少一个小时;以及
6.将软化水加入至该混合物,确定全部的固体完全溶解并均匀混合。继续搅拌至少30分钟。
进行一系列的银测试浴。定性及定量地观察防锈性及可焊性。将板保持在硫室中2.5小时。视觉观察生锈,然后利用连续电化学还原分析(SERA)来定量。使用波焊机来评测可焊性。结果示于表1。
表1.抗锈性及可焊性的定性及定量评测
样品 | 目视生锈 | 总生锈厚度(埃) | 可焊性百分比 | 润湿性 |
浸渍银对照组 | 蓝色和彩虹色 | 超过2000 | 100 | 不润湿 |
后浸渍处理的浸渍银 | 银色 | 少于50 | 100 | 均匀润湿 |
进行研究以确定最理想的聚合物浴浓度及发展出有效率的测试,以证明该碱性聚合物涂料已在该基材上并起作用。使用2英寸乘2英寸的标准镀银试样。将经聚合物涂料处理的试样与对照组(镀银试样,无碱性聚合物涂料)通过硫室进行处理1.5小时。结果示于表2。
表2.碱性聚合物涂料浴的最理想浓度
聚合物涂料浴(浓度,%) | 硫室(时间=1.5小时)吹干 | 10~20%氯化铁溶液(IPC生锈测试)(20秒~10分钟) |
1% | 略微生锈 | |
5% | O.K. | 通过 |
10% | O.K. | 通过 |
15% | O.K. | 通过 |
20% | O.K. | 通过 |
对照组,无聚合物涂料 | 严重 | 立即破坏 |
此外,将置于硫室中24小时的样品焊接并将其放回硫室处理另外的24小时。对照组样品会生锈,而涂布聚合物的面板无变化。两个样品的焊接率均为100%,且在第二个24小时周期后,经该碱性聚合物涂布的面板仍然无变化,而对照组面板显示出额外的生锈。
Claims (10)
1.一种改善金属表面耐电迁移性同时维持金属表面可焊性的方法,包括步骤:
a)将金属表面与浸渍镀银溶液或化学镀银溶液接触,在该金属表面上产生银镀层;以及
b)随后将该镀银表面与聚合物涂布溶液接触,该聚合物涂布溶液包含从由乙烯基共聚物、丙烯酸共聚物、乙烯基聚合物、丙烯酸聚合物和前述物质的混合物组成的组中选出的一种材料;
其中该银镀层与没有经过步骤(b)处理的同样的银镀层相比具有更低的电迁移趋势。
2.根据权利要求1的方法,其中该金属表面包含铜。
3.根据权利要求1的方法,其中该聚合物涂布溶液中含有合计量为20~50重量%的乙烯基共聚物或乙烯基聚合物。
4.根据权利要求1的方法,其中该聚合物涂布溶液中含有合计量为30~45重量%的乙烯基共聚物或乙烯基聚合物。
5.根据权利要求1的方法,其中该聚合物涂布溶液中含有合计量为5~30重量%的丙烯酸共聚物或丙烯酸聚合物。
6.根据权利要求1的方法,其中该聚合物涂布溶液中含有合计量为30~45重量%的丙烯酸共聚物或丙烯酸聚合物。
7.根据权利要求1的方法,其中该涂布溶液还包含从由三唑、咪唑和前述物质的组合组成的组中选出的一种材料。
8.根据权利要求7的方法,其中该三唑或咪唑是从由苯并三唑、苯并咪唑、咪唑、组氨酸和前述物质的组合组成的组中选出的一种材料。
9.根据权利要求7的方法,其中该涂布溶液中含有0.5~5重量%的三唑或咪唑。
10.根据权利要求1的方法,其中该聚合物涂布溶液还包含氨。
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- 2004-03-15 CN CNB2004800098108A patent/CN100371089C/zh not_active Expired - Lifetime
- 2004-03-15 JP JP2006501235A patent/JP2006522216A/ja active Pending
- 2004-03-15 EP EP04720786.5A patent/EP1613440B1/en not_active Expired - Lifetime
- 2004-03-15 ES ES04720786.5T patent/ES2656779T3/es not_active Expired - Lifetime
- 2004-03-15 WO PCT/US2004/007773 patent/WO2004094682A2/en active Application Filing
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Also Published As
Publication number | Publication date |
---|---|
EP1613440A2 (en) | 2006-01-11 |
CN1774304A (zh) | 2006-05-17 |
WO2004094682A2 (en) | 2004-11-04 |
TWI241872B (en) | 2005-10-11 |
ES2656779T3 (es) | 2018-02-28 |
EP1613440A4 (en) | 2006-11-02 |
EP1613440B1 (en) | 2017-11-15 |
US6773757B1 (en) | 2004-08-10 |
WO2004094682A3 (en) | 2005-01-20 |
JP2006522216A (ja) | 2006-09-28 |
WO2004094682B1 (en) | 2005-02-17 |
TW200425810A (en) | 2004-11-16 |
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