CN1331907C - 改性的反应性热熔胶粘剂及其应用 - Google Patents
改性的反应性热熔胶粘剂及其应用 Download PDFInfo
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- CN1331907C CN1331907C CNB028195760A CN02819576A CN1331907C CN 1331907 C CN1331907 C CN 1331907C CN B028195760 A CNB028195760 A CN B028195760A CN 02819576 A CN02819576 A CN 02819576A CN 1331907 C CN1331907 C CN 1331907C
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Abstract
本发明涉及一种单组分、湿固化的热熔胶粘剂组合物,该组合物基于得自二异氰酸酯或聚异氰酸酯和聚醚型多元醇、结晶或部分结晶的聚酯型多元醇、和得自烯属不饱和单体的低分子量聚合物、以及选择性的羟基化增粘树脂的反应产物;该组合物适用于高强度和抗老化地将塑料型材与单层或多层丙烯酸酯膜胶合。
Description
本发明涉及改性的、单组分、湿固化的聚氨酯热熔胶粘剂,及其在将膜层压到塑料、木材、衍生木材制品、金属、石头或类似材料上的应用。
通常对物体表面施用有色的或带有图案的表面膜,所述物体为诸如,例如窗框架;门;塑料型材或外壳、木材、衍生木材制品、金属、石头或类似材料,目的在于一方面保护物体表面免受破坏性影响,诸如,例如腐蚀、光或机械作用引起的褪色;应用表面膜的另一个原因是使物体表面更引人注意。
例如,如果使用带有适当图案的膜,可给人以贵重木材的印象,即使实际使用的材料由于其外观、结构、表面或颜色不适合这一应用。因此,如此应用的表面膜可保护物体表面免受环境影响,诸如,例如水或潮气的作用、温度或光特别是日光的改变、或大气中的环境有害物质。
在建造窗和门时,塑料型材得到广泛应用,特别是热塑性材料如聚氯乙烯(PVC)、聚丙烯(PP)和丙烯腈/丁二烯/苯乙烯共聚物(ABS)的异型材,无论用于完全型材、空心型材或核心型材,因为它们容易通过压出工艺制备、成本低和使用性好。在PVC的情况中,本文使用的PVC可为塑化的、或半刚性、或特别是刚性PVC。使用的表面膜可为PVC膜、CRL(连续压力层合体)和HPL(高压层合体)膜、(印刷)纸、饰面板或其它片状结构,通常厚度为0.1到1.0mm。对于有效的生产工艺,需要胶粘剂在使用之后的很短时间具有高的初始粘合强度,并且其最终粘合强度更大。这些需要被反应性聚氨酯热熔胶粘剂以优异的方式满足,但为此需要在许多塑料表面上用增粘层预处理。据说应用增粘层可得到高的生产率并且仍然是环境友好的。
本发明的增粘层可借助于等离子体或电晕预处理实现,但也可施用底漆形式的增粘底漆,例如水性底漆,如德国专利DE-A-19826329中公开的。
塑料或塑料膜表面的增粘表面预处理也可借助于WO99/46352所述的清洁组合物实施。在这种情况中,在胶合之前也可对塑料的清洁表面进行进一步的机械、物理、化学或电化学预处理,具体而言,这可以是应用例如上述类型的增粘剂或底漆,或可通过燃烧或电晕处理进行预处理。
对于许多的表面膜与上述塑料、衍生木材制品或铝材料基材的胶合可以得到完全满意的结果。
在外部应用的领域中,特别耐候和光稳定的更新的膜被越来越多地提出来。特别地,这些膜是基于(甲基)丙烯酸酯,特别是多种聚甲基丙烯酸酯的均聚物和共聚物的混合物的膜。使用聚(甲基)丙烯酸酯膜的一个优点在于,通过适当选择共聚用单体可容易地生产不同硬度(从脆硬到高挠性)的膜。另一个优点见于以下事实,可使用常规的、高度耐晒的有机颜料亦或含铁、铬或镍的颜料使这些膜着色。
已知这些聚(甲基)丙烯酸酯膜的耐候和耐UV性良好。最近提出了被构建成多层膜的表面膜,以进一步改善其对光和候化的稳定性。因此,欧洲专利EP-A-343491提出了一种(甲基)丙烯酸酯基膜的多层膜,其具有象玻璃一样透明的聚丙烯酸酯顶层膜和另外的象玻璃一样透明的聚偏氟乙烯(PVDF)或聚氟乙烯(PVF)保护膜。
这些单层或多层的基于丙烯酸酯或甲基丙烯酸酯的表面膜确实对光和候化具有优异的抵抗性,但用至今已知的热熔胶粘剂使这些膜永久耐候地胶合于上述热塑性聚合物、木材、铝和类似材料上是不可能的。
考虑上述现有技术,本发明人的目的是提供单组分、湿固化的聚氨酯热熔胶粘剂,其特别用于胶合单层或多层的基于丙烯酸酯或甲基丙烯酸酯聚合物或共聚物的表面膜。本发明目的的实现从权利要求书可以看出。
本发明基本上包括,提供一种单组分、湿固化的聚氨酯热熔胶粘剂,其包括至少一种具有反应性异氰酸酯基团的反应产物,所述反应产物是通过使至少一种二异氰酸酯或聚异氰酸酯与一种或多种聚醚型多元醇、部分结晶或结晶的聚酯型多元醇和/或得自烯属不饱和单体的低分子量聚合物和选择性的增粘树脂反应而获得的。
本发明还提供上述聚氨酯热熔胶粘剂的应用,用于使单层或多层(甲基)丙烯酸酯表面膜胶合到热塑性塑料、木材或铝基材上。本文所用的热塑性塑料尤其是PVC、丙烯、ABS,其可为新出厂塑料或为回收产品、或选择性地为新出厂塑料和回收产品的混合物。本发明的聚氨酯热熔胶粘剂特别用于胶合具有基膜和表面膜的多层膜,所述基膜是基于着色的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物,所述表面膜是甲基丙烯酸酯共聚物、聚偏氟乙烯或聚氟乙烯或其组合。
本发明还提供一种工艺,用于向热塑性塑料、木材或铝的成形制品上层压上述类型的单层或多层膜,本工艺特征在于以下的主要步骤:
a)对单层或多层膜的待胶合面进行表面处理,通常通过燃烧、电晕处理、施用底漆或用清洁剂预处理的方法、或上述处理方法的组合;
b)然后把热熔胶粘剂施用于表面膜;
c)成形制品的表面选择性地通过施用底漆、使用清洁剂或通过燃烧或电晕处理进行预处理,然后选择性地,通过选择性地施加热使易挥发组分蒸发。成形制品表面的表面预处理也可由一个或多个上述方法的组合组成;
d)然后使膜结合到成形制品上,选择性地通过适当手段施压于膜上。
在特别有利的情况中,表面膜的表面预处理或成形制品的预处理可被省略。
为得到热熔胶粘剂与基材表面的良好润湿,可在施用胶粘剂之前或在结合之前加热膜和/或成形制品。
原则上所有已知的单体二异氰酸酯适都用于聚氨酯热熔胶粘剂的制备。本发明中单体二异氰酸酯或聚异氰酸酯是那些分子量低于500的芳香族、脂肪族或脂环族二异氰酸酯。适当的芳香族二异氰酸酯的例子是甲苯二异氰酸酯(TDI)的所有异构体,其或为异构体纯形式或为几种异构体的混合物;萘-1,5-二异氰酸酯(NDI);萘-1,4-二异氰酸酯(NDI);二苯甲烷-4,4’-二异氰酸酯(MDI);二苯甲烷-2,4’-二异氰酸酯;及二苯甲烷-4,4’-二异氰酸酯(MDI)与2,4’-异构体的混合物;苯二亚甲基二异氰酸酯(XDI);4,4’-二苯基-二甲基甲烷二异氰酸酯;二或四烷基-二苯基甲烷二异氰酸酯;4,4’-二苄基二异氰酸酯;1,3-亚苯基二异氰酸酯和1,4-亚苯基二异氰酸酯。适当的脂环族二异氰酸酯的例子是上述芳香族二异氰酸酯的氢化产物,诸如,例如二环己基甲烷-4,4’-二异氰酸酯(H12MDI)、1-异氰酸酯基甲基-3-异氰酸酯基-1,5,5-三甲基环己烷(异佛尔酮二异氰酸酯,IPDI)、环己烷-1,4-二异氰酸酯、氢化苯二亚甲基二异氰酸酯(H6XDI)、1-甲基-2,4-二异氰酸酯基环己烷、间-或对-四甲基苯二亚甲基二异氰酸酯(m-TMXDI、p-TMXDI)和二聚脂肪酸二异氰酸酯。脂肪族二异氰酸酯的例子是四甲氧基丁烷-1,4-二异氰酸酯、丁烷-1,4-二异氰酸酯、己烷-1,6-二异氰酸酯(HDI)、1,6-二异氰酸酯基-2,2,4-三甲基正己烷、1,6-二异氰酸酯基-2,4,4-三甲基己烷、赖氨酸二异氰酸酯和1,12-十二烷基二异氰酸酯基(C12DI)。
优选使用的异氰酸酯是MDI。
本文使用本身已知的聚丙二醇或聚丁二醇作为聚醚型多元醇,例如二-和/或三官能聚丙二醇,其每个分子分别具有二或三个羟基,分子量为400到20,000,优选1000到6000。也可使用环氧乙烷和环氧丙烷的无规和/或嵌段共聚物。优选使用的其它聚醚是聚丁二醇,其通过例如四氢呋喃的酸聚合来制备,本文的聚丁二醇的分子量为600到6000,优选800到5000。
优选地,使用至少两种聚醚型多元醇,一种聚醚型多元醇的平均分子量在1000以上、和一种聚醚型多元醇的平均分子量在1000以下,优选后者的分子量为400到800。代替聚醚型多元醇,也可使用特别是低分子量的多元醇、烷撑二醇,诸如,例如丁二醇、己二醇、辛二醇、癸二醇或十二烷二醇。
适当的聚酯型多元醇是结晶或部分结晶的聚酯型多元醇,其可通过使二羧酸或三羧酸与低分子量的二醇或三醇缩合来制备,所述二羧酸或三羧酸是诸如例如己二酸、癸二酸、戊二酸、壬二酸、辛二酸、十一烷二酸、十二烷二酸、3,3-二甲基戊二酸、对苯二酸、间苯二酸、环己烷邻二甲酸、二聚脂肪酸或其混合物,所述二醇或三醇是诸如,例如乙二醇、丙二醇、二甘醇、三甘醇、二丙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇、二聚脂肪醇、丙三醇、三羟甲基丙烷或其混合物。
本发明使用的另一组多元醇为基于ε-己内酯的聚酯,也称为“聚己酸内酯”。
然而,也可使用油化学来源的聚酯型多元醇。可通过例如使脂肪混合物的环氧化甘油三羧酸酯完全开环来制备,和随后将甘油三羧酸酯衍生物部分酯交换得到烷基具有1到12个碳原子的烷基酯多元醇来制备这种聚酯型多元醇,所述脂肪混合物至少部分包括烯属不饱和脂肪酸与一种或多种1到12个碳原子的醇。其它适当的多元醇是聚碳酸酯型多元醇和二聚物型二醇(Henkel),以及蓖麻油及其衍生物。
上述聚醚型多元醇和聚酯型多元醇的分子量是数均分子量,其通常是通过从羟基数计算确定的。
本发明的“得自烯属不饱和单体的低分子量聚合物”是从一种或多种单体制备的聚合物,所述单体选自丙烯酸;甲基丙烯酸;丙烯酸或甲基丙烯酸的C1-C10烷基酯;(甲基)丙烯酸与乙二醇醚,如与甲氧基乙醇、乙氧基乙醇、丙氧基乙醇和/或丁氧基乙醇的酯;乙烯酯,如乙酸乙烯酯、丙酸乙烯酯和多支链单羧酸的乙烯酯,诸如,例如versatic酸(一种有支链的烷烃羧酸,Shell Chemie产品)的乙烯酯;乙烯醚;反丁烯二酸酯;顺丁烯二酸酯;苯乙烯;烷基苯乙烯;丁二烯或丙烯腈及其混合物。
在一个优选实施方案中,这些低分子量聚合物具有活泼氢基团,其为羟基形式、或为伯胺或仲胺基形式,使得这些低分子量聚合物可一起化学键合进入热熔胶粘剂的聚合物基质内。低分子量聚合物通常是通过上述单体的自由基聚合或共聚合制备。为了引入活泼氢基团,(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯、或丙烯酸或甲基丙烯酸与二醇低聚物或聚合物的酯,如二、三、四和/或聚乙二醇可与上述单体聚合。代替上述羟基官能的(甲基)丙烯酸酯,也可一起使用相应的氨基官能的共聚用单体。得自烯属不饱和单体的低分子量聚合物的分子量范围为10000-150000道尔顿、优选为20000-80000道尔顿。本文中平均分子量根据标准凝胶渗透色谱(GPC)测定,平均分子量的测量对于通过自由基聚合获得的共聚物而言是常规的,标准凝胶渗透色谱有时也称作“体积排阻色谱”(SEC)。为此,平均分子量根据已鉴定分子量的外标聚苯乙烯计算。
如果使用OH-官能聚合物,这些聚合物应具有0.5-20个,优选1-15个OH数(DIN53783)。特别适用的带有活泼氢基团的低分子量聚合物在WO99/28363第13-14页中公开。该公开作为本申请的一个组成部分。
可用的增粘树脂是例如松香酸、松香酸酯、萜烯树脂、萜烯-苯酚树脂、苯酚改性的苯乙烯树脂、烃类树脂的用酚改性的α-甲基苯乙烯聚合物。
在一个优选实施方案中,这些增粘树脂可含有活泼氢原子,使得这些增粘树脂在与二异氰酸酯或聚异氰酸酯反应期间可被引入到热熔胶粘剂的胶粘剂基质中。这些增粘树脂的具体实例是松香酸的羟基官能酯、或也可是羟基化萜烯-苯酚树脂。
在一个特别优选的实施方案中,不含或含有极少量的单体、低分子量二异氰酸酯的聚氨酯组合物可用作本发明的聚氨酯热熔胶粘剂。这些热熔胶粘剂组合物是WO001/40342的主题。该申请中有关低残余单体含量的组合物的具体描述特别地作为本申请的主体。
本发明的热熔胶粘剂可进一步另外包括稳定剂、增粘添加剂、填料、颜料、增塑剂和/或催化剂。
本发明的“稳定剂”可以理解为,一方面,其是实现制备、贮存或应用期间聚氨酯预聚物粘度稳定性的稳定剂。单官能酰基氯、单官能高反应性异氰酸酯以及例如非腐蚀性无机酸也适用于本发明,例如苯甲酰氯、甲苯磺酰基异氰酸酯、硫酸或亚磷酸。抗氧化剂、UV稳定剂或水解稳定剂可进一步理解为是本发明的稳定剂。这些稳定剂的选择一方面取决于组合物中的主要成分,另一方面取决于应用条件和固化物上的预期负荷。如果聚氨酯预聚物主要从聚醚单元构建,则抗氧化剂、选择性地与UV稳定剂组合,是非常必要的。这些稳定剂的实例是市售的立体受阻苯酚和/或硫醚和/或取代的苯并三唑或HALS(“受阻胺光稳定剂”)的立体受阻胺型。
如果聚氨酯预聚物的主要组分包括聚酯单元,则可使用水解稳定剂,如碳二亚胺类型的水解稳定剂。
系统中选择性含有的催化剂可以以已知方式促进聚氨酯预聚物在其制备和/或在施用胶粘剂之后的湿交联期间形成。本发明可使用的适当的催化剂具体是上述WO01/40342第11-13页中所述的有机锡和/或胺催化剂,其中也描述了其用量。
在特别优选的实施方案中,本发明的聚氨酯热熔胶粘剂可以包括以下组分:
-5-15重量%,优选8-12重量%的二异氰酸酯,优选二苯基甲烷二异氰酸酯;与
-20-40重量%,优选25-40重量%的双官能聚丙二醇,分子量为2000-6000;
-2-8重量%的聚丙二醇或烷撑二醇,分子量为200-600;
-15-30重量%,优选20-25重量%的结晶或部分结晶的聚酯型多元醇;
-10-35重量%,优选15-30重量%的烯属不饱和单体的低分子量聚合物,优选具有羟基;
-2-8重量%的优选羟基化的增粘树脂;
-0.01-0.1重量%的上述类型的酸稳定剂。
本文中上述组分的总和为100重量%。
原则上,上述反应性产物可单独地通过与二异氰酸酯反应来制备,然后以这种方式单独制备的异氰酸酯官能反应物可以需要的量进行混合。其它可能的制备方法在WO99/28363第16-17页描述,其作为公开的组成部分引入本申请。
在一个优选实施方案中,本发明的聚氨酯热熔胶粘剂可以以一步反应制备;或者如果使用官能性低分子量聚合物,则将全部低分子量聚合物混入少量的一种或多种多元醇中,然后加入全部聚异氰酸酯而制备。在反应结束后,加入余下的多元醇或多元醇混合物。
原则上,本发明通过以下实施例进行描述,所选实施例不构成对本发明保护范围的限制。这些实施例仅仅表示本发明的热熔胶粘剂的作用方式的模式,以及这些热熔胶粘剂将一层或多层基于丙烯酸酯或甲基丙烯酸酯聚合物的表面膜胶合到塑料型材上,如通常用于窗构建中的塑料型材上的优点。
除非另外说明,在以下实施例中,所有的量为重量百分数或重量份数。
实施例
实施例1
在可加热搅拌的罐中,从以下组分制备具有游离异氰酸酯基团的反应性热熔胶粘剂组合物:
聚丙二醇,MW2000,OH数56, 32.18%
聚丙二醇,MW400,OH数260, 4.87%
基于己二酸己二醇酯的部分结晶的聚酯,OH数30.5 21.46%
丙烯酸共聚物,MW34000,OH数2.1 24.38%
羟基化的增粘树脂,OH数75 4.87%
4-甲苯磺酰基异氰酸酯 0.03%
4,4’-二苯基甲烷二异氰酸酯 12.21%
在异氰酸酯基团与羟基反应结束后,以常规方法将热熔胶粘剂组合物引入到防湿密闭容器中,其具有以下特征值:
NCO含量:1.15%;熔融物在130℃的粘度:17Pa.s,用装备有Thermosel的Broolfield粘度计测量。
用于层压PVC窗型材时,实施例1的反应性热熔胶粘剂用于向标准PVC窗型材上胶合一种多层的基于着色丙烯酸膜的窗装饰膜,所述窗装饰膜具有透明、无色的丙烯酸/聚偏氟乙烯共挤塑膜作为表面层。丙烯酸酯侧用作装饰膜的胶合侧。在Friz、DTC-2型的标准型材装铠机(sheathing machine)中进行胶合,PVC型材已用Henkel Dorus的溶剂性底漆6-B-23进行了预处理。装铠机的刀隙为50μm,热熔胶粘剂温度为130℃,PVC型材温度为55℃。在10分钟、1小时、1天和7天以及老化(7天,在70℃与水接触)后测量胶合剥离强度。结果总结于下表。
在所述时间后的剥离强度(N/20mm)
实施例 | 膜 | 胶粘剂 | 10分钟 | 1小时 | 1天 | 7天 | 7天/70℃、H2O老化后 |
2 | FAST | 实施例1 | 7 | 20 | 48,FT | 50,FT | 81,FT |
3 | FAST | 实施例1 | 4 | 20 | 75,FT | 76,FT | - |
4 | FAST | QR5305 | 5 | 9 | 42,AF-F | 51,AF-F | 40,AF-F |
5 | FAST | QR3530-24 | 2 | 8 | 22 | 46,AF-F | 40,AF-F |
6 | MBAS2 | 实施例1 | 6 | 16 | 72,FT | 86,FT | 67,FT |
7 | MBAS2 | QR5305 | 3 | 4 | 42 | 84,FT | 43 |
QR5305=Purmelt QR5305,Henkel KGaA
QR5305-24=Purmelt QR3530-24,Henkel KGaA
FAST=基于着色丙烯酸膜的多层膜,Renolit
MBAS2=标准PVC膜
FT=膜撕破但没有剥离
AF-F=与膜的粘合断裂
无结果=剥离,伴随粘着断裂
从以上结果可见,即使在老化后,当基于丙烯酸基膜的高度光稳定的多层膜用于胶合时,实施例1的热熔胶粘剂在初始剥离强度和最终剥离强度方面均优于市售的聚氨酯热熔胶粘剂(QR5305)和市售的基于丙烯酸酯的热熔胶粘剂(QR3530-24)。同时,本发明实施例1的热熔胶粘剂也适用于胶合常规的PVC膜(参见实施例6)。
Claims (10)
1.单组分、湿固化的聚氨酯热熔胶粘剂,其包括至少一种具有反应性NCO基团的反应产物,所述胶粘剂可通过以下组分的反应获得:
a)至少一种二异氰酸酯或聚异氰酸酯;与
b)聚醚型多元醇,其包括
b1)20-40重量%的平均分子量在1000以上的至少一种二元醇和
b2)2-8重量%的平均分子量在1000以下的至少一种聚醚型多元醇和/或烷撑二醇;
c)结晶或部分结晶的聚酯型多元醇和
d)得自烯属不饱和单体的低分子量聚合物;和
e)可选择的增粘树脂。
2.权利要求1的聚氨酯热熔胶粘剂,其特征在于低分子量聚合物具有活泼氢基团。
3.权利要求1或2的聚氨酯热熔胶粘剂,其特征在于增粘树脂具有活泼氢基团。
4.权利要求1-3的聚氨酯热熔胶粘剂的应用,其用于将单层或多层的基于聚(甲基)丙烯酸酯的表面膜胶合到热塑性塑料、木材或铝基材上。
5.权利要求4的应用,其中,所述的热塑性塑料选自PVC、聚丙烯和ABS。
6.权利要求4的应用,其特征在于多层膜由基于着色的(甲基)丙烯酸酯聚合物或共聚物的基膜和无色的甲基丙烯酸酯共聚物、聚偏氟乙烯或聚氟乙烯的表面膜构建而成。
7.将单层或多层的基于聚(甲基)丙烯酸酯的表面膜层压到聚氯乙烯(PVC)、聚丙烯、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、木材或铝的成形制品上的方法,其特征在于以下的主要工艺步骤:
b)将权利要求1-3的热熔胶粘剂施用到表面膜上;和
d)将所述膜与成形制品结合,选择性地伴随施压。
8.权利要求7的方法,其特征在于,在步骤b)之前,还包括步骤:
a)通过电晕处理、施用底漆或使用清洁剂的预处理、以及可选的将膜预热,对表面膜的待胶合面进行表面处理。
9.权利要求7或8的方法,其特征在于,在步骤b)和d)之间,还包括步骤:
c)通过施用底漆或使用清洁剂处理对成形制品的表面进行预处理,然后选择性地,通过选择性的施加热使易挥发组分蒸发;然后选择性地进行电晕处理或燃烧。
10.可根据权利要求7-9生产的层压成形制品在门、建筑物正面组件以及门和窗框架中的应用。
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- 2002-09-26 KR KR10-2004-7004900A patent/KR20040045471A/ko not_active Application Discontinuation
- 2002-09-26 EP EP02772349A patent/EP1432748A1/de not_active Withdrawn
- 2002-09-26 PL PL02367492A patent/PL367492A1/xx not_active Application Discontinuation
- 2002-09-26 CA CA002462830A patent/CA2462830A1/en not_active Abandoned
- 2002-09-26 BR BR0213123-4A patent/BR0213123A/pt not_active IP Right Cessation
- 2002-09-26 CN CNB028195760A patent/CN1331907C/zh not_active Expired - Fee Related
- 2002-09-26 MX MXPA04003025A patent/MXPA04003025A/es active IP Right Grant
- 2002-09-26 JP JP2003534472A patent/JP2005504867A/ja active Pending
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Also Published As
Publication number | Publication date |
---|---|
MXPA04003025A (es) | 2004-07-05 |
CN1564835A (zh) | 2005-01-12 |
EP1432748A1 (de) | 2004-06-30 |
BR0213123A (pt) | 2004-09-21 |
US20050033004A1 (en) | 2005-02-10 |
PL367492A1 (en) | 2005-02-21 |
CA2462830A1 (en) | 2003-04-17 |
US7300996B2 (en) | 2007-11-27 |
WO2003031490A1 (de) | 2003-04-17 |
KR20040045471A (ko) | 2004-06-01 |
DE10149142A1 (de) | 2003-04-24 |
JP2005504867A (ja) | 2005-02-17 |
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