CN1238391C - 新型阳离子缔合聚氨酯及其作为增稠剂的应用 - Google Patents
新型阳离子缔合聚氨酯及其作为增稠剂的应用 Download PDFInfo
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Abstract
本发明涉及式(I)的新型两亲阳离子缔合聚氨酯:R-X-(P)n-[L-(Y)m]r-L’-(P’)p-X’-R’ (I)其中:R和R’相同或不同,表示疏水基团或氢原子;X和X’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团或L”基团;L、L’和L”相同或不同,表示从二异氰酸酯衍生的基团;P和P’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团;Y表示亲水基团;r为1-100的整数,优选在1-50,更优选在1-25;n、m和p具有相互独立的值,在0-1000之间;该分子含有至少一个质子化的或季铵化的胺官能团和至少一个疏水基团。本发明还涉及这些聚氨酯在局部应用的化妆品组合物中作为增稠剂或胶凝剂的应用。
Description
技术领域
本发明涉及新型水溶性或水分散性的两亲阳离子缔合的聚氨酯以及其在局部应用特别是美容或治疗用途的组合物中的应用。
背景技术
与本发明缔合聚氨酯相关的术语“水溶性的”是指该聚合物在室温下的水中的溶解度至少为1%重量,也就是说在该浓度下没有肉眼可检测出的沉淀,溶液特别清澈、均一。
术语“水分散性的”聚氨酯是指聚合物混悬在水中,自发形成具有平均粒径的小球,通过Coulter型装置测定光散射,粒径在5nm-600nm,尤其在5nm-500nm。
通过聚合物的水性介质增稠和/或形成胶体长时间一直是一重要研究课题,特别是在化妆品和药物领域。通过水溶性聚合物产生理想的增稠效果通常需要高摩尔量和高的流体动力学体积。水性介质形成凝胶被认为是通过线性聚合物交联或通过双官能团和多功能团单体共聚得到的三维聚合物网络的结果。然而,应用这些摩尔量非常高的聚合物会存在很多问题,如得到的凝胶结构不很理想和难于扩散。
有一种很好地用作增稠剂的方法,聚合物能够相互或与其它分子或颗粒可逆地缔合。该物理缔合导致形成具有触变作用或剪切稀化的大分子系统,这就是说该系统粘度基于它们受到的剪切力。
这些能够相互或与其它分子可逆地缔合的聚合物被称为“缔合聚合物”。涉及的相互作用力在本质上相差很远,例如静电性质、氢键类型或疏水作用。
缔合聚合物的一个具体例子是两亲聚合物,也就是说聚合物包括一个或多个亲水部分,其可以使它们溶于水,还包括一个或多个疏水区域,通过它们聚合物相互作用,相互或与其它分子结合。
缔合聚合物特别是缔合的聚氨酯已被推荐在化妆品中应用。然而,这些聚合物的流变学和化妆品的性质仍不适宜。
已发现新的一类水溶性或水分散性的两亲阳离子缔合的聚氨酯,该聚氨酯具有优异的增稠性质,并具有良好的化妆品性质。
该优异的增稠性质能够使聚合物的用量很少。该优点有可能改善含有其组合物的结构。
应用本发明的缔合聚氨酯得到的凝胶手感良好,并且易于扩散。
发明内容
本发明的一个主题是一类新的水溶性或水分散性的两亲阳离子缔合的聚氨酯。
本发明的另一个主题是含有至少一种水溶性或水分散性的两亲阳离子缔合的聚氨酯的化妆品组合物。
本发明的第三个主题是这些聚氨酯在局部化妆或治疗应用的组合物中作为增稠剂或胶凝剂的应用。
读完说明书和其后的实施例可以显而易见地发现本发明的其它主题。
按照本发明的该类水溶性或水分散性的两亲阳离子缔合的聚氨酯可以通过下式(I)表示:
R-X-(P)n-[L-(Y)m]r-L’-(P’)p-X’-R’(I)
其中:
R和R’相同或不同,表示疏水基团或氢原子;
X和X’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团或L”基团;
L、L’和L”相同或不同,表示从二异氰酸酯衍生的基团;
P和P’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团;
Y表示亲水基团;
r为1-100的整数,优选在1-50,更优选在1-25;
n、m和p具有相互独立的值,在0-1000之间。
该分子含有至少一个质子化的或季铵化的胺官能团和至少一个疏水基团。
在本发明聚氨酯的优选实施方案中,唯一的疏水基团为链末端的R和R’基团。
按照本发明的一类优选的阳离子缔合聚氨酯为对应于上式I的那些聚合物,其中
R和R’独立表示疏水基团;
X和X’分别表示L”基团;
n和p的值为1-1000,
以及L、L’、L”、P、P’、Y和m具有上述的含义。
按照本发明的另一类阳离子缔合聚氨酯为对应于上式I的那些聚合物,其中R和R’独立表示疏水基团,X和X’分别表示L”基团,n和p的值为0,以及L、L’、L”、Y和m具有上述的含义。
n和p的值为0表示这些聚合物不含有具有在缩聚中结合在聚合物中的胺官能团的单体衍生的单元。这些聚氨酯的质子化的胺官能团产生于链末端过量的异氰酸酯官能团的水解,然后通过含有疏水基团的烷基化剂对形成的伯胺官能团进行烷基化,也就是说,RQ或R’Q型化合物,其中R和R’如上所定义,Q表示离去基团,如卤离子、硫酸根等。
按照本发明的另一类优选的阳离子缔合聚氨酯为对应于上式I的那些聚合物,其中
R和R’独立表示疏水基团;
X和X’独立表示含有季铵的基团;
n和p的值为0,
以及L、L’、Y和m具有上述的含义。
本发明的两亲阳离子缔合的聚氨酯的数均分子量优选在400-500000之间,特别是在1000-400000之间,理想在1000-300000之间。
术语“疏水基团”被理解为具有饱和或不饱和、直链或支链烃链的基团或聚合物,其中烃链可以含有一个或多个杂原子如P、O、N或S,或具有全氟化或硅酮链的基团。当其表示烃基,疏水基团含有至少10个碳原子,优选10-30个碳原子,特别是12-30个碳原子,更优选是18-30个碳原子。
烃疏水基团优选来源于单官能团化合物。
作为实例,疏水基团可以从脂肪醇产生,如十八烷醇、十二烷醇或癸醇。疏水基团还可以是烃聚合物,例如聚丁二烯。
当X和/或X’表示含有叔胺或季铵的基团,X和/或X’可以表示下式之一:
X表示:
X’表示:
其中:
R2表示具有1-20个碳原子的直链或支链亚烷基,其可以含有也可以不含有饱和或不饱和环,或亚芳基,有可能一个或多个碳原子被选自N、S、O或P的杂原子取代;
R1和R3相同或不同,表示直链或支链C1-C30烷基或烯基或芳基,有可能至少一个碳原子被选自N、S、O或P的杂原子取代;
A’为生理可接受的平衡离子。
L、L’和L”表示下式的基团:
其中
Z表示-O-,-S-或-NH-;
以及R4表示具有1-20个碳原子的直链或支链亚烷基,其可以含有也可以不含有饱和或不饱和环,或亚芳基,有可能一个或多个碳原子被选自N、S、O和P的杂原子取代。
含有一个胺官能团的P和P’可以表示下式中的至少一个:
其中:
R5和R7与上述定义的R2具有相同的含义;
R6、R8和R9与上述定义的R1和R3具有相同的含义;
R10表示直链或支链亚烷基基团,其任选是不饱和的,可以含有一个或多个选自N、O、S和P的杂原子;
A’为生理可接受的平衡离子。
关于Y的含义,术语“亲水基团”被理解为水溶性的聚合或非聚合基团。
当不涉及聚合物时,顺便提及作为实例的有乙二醇、二甘醇和丙二醇。
当与本发明的优选实施方案相一致,涉及亲水聚合物时,顺便提及作为实例的有聚醚、磺化聚酯、磺化聚酰胺或这些聚合物的混合物。该亲水化合物优选为聚醚,特别是聚环氧乙烷或聚环氧丙烷。
按照本发明式I的两亲阳离子缔合的聚氨酯可以从二异氰酸酯和具有不稳定氢官能团的多种化合物制备。具有不稳定氢的官能团可以是醇、伯或仲胺、或硫醇官能团,与二异氰酸酯官能团反应后,分别得到聚氨酯、聚脲和聚硫脲。术语“聚氨酯”被选择表示本发明的新型缔合聚合物,包括三类聚合物,即严格意义上的聚氨酯、聚脲和聚硫脲,和它们的共聚物。
参与制备本发明式I聚合物的第一类化合物为含有至少一个具有胺官能团的单元的化合物。该化合物可以是多官能团的,但是该化合物优选是双官能团,也就是说,按照本发明的优选实施方案,该化合物含有两个不稳定氢原子,例如带有羟基、伯胺、仲胺或硫醇官能团。还可以应用多官能团和双官能团的混合物,其中多官能团的比例较低。
如上所述,该化合物可以含有超过一个的具有胺官能团的单元。因此聚合物带有具有胺官能团的重复单元。
该类化合物可以由下式之一表示:
HZ-(P)n-ZH 或 HZ-(P’)p-ZH
其中Z、P、P’、n和p如上所定义。
顺便提及,具有胺官能团基团的化合物的例子有N-四基二乙醇胺、N-(叔丁基)二乙醇胺或N-磺基乙基二乙醇胺。
参与制备按照本发明式I聚合物的第二类化合物为对应于下式的二异氰酸酯:
O=C=N-R4-N=C=O
其中R4如上所定义。
顺便提及,作为例子的有亚甲基二苯基二异氰酸酯、亚甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、萘二异氰酸酯、丁烷二异氰酸酯或己烷二异氰酸酯。
参与制备按照本发明式I聚合物的第三类化合物为疏水化合物,以形成式I聚合物的末端疏水基团。
该化合物组成为疏水基团和具有不稳定氢的官能团,例如羟基、伯胺、仲胺或硫醇官能团。
作为例子,该化合物可以是脂肪醇,如十八烷醇、十二烷醇或癸醇。当该化合物含有聚合物链时,它例如可以是α-羟基氢化聚丁二烯。
按照本发明式I聚合物的疏水基团还可以从含有至少一个叔胺单元的叔胺化合物的季铵化反应制备。因此,该疏水基团通过季铵化剂被引入。该季铵化剂为RQ或R’Q型化合物,其中R和R’如上所定义,Q表示离去基团,如卤离子、硫酸根等。
本发明的两亲阳离子缔合聚合物可以另外含有亲水序列。该序列由参与制备该聚合物的第四类化合物所提供。该化合物可以是多官能团的。优选是双官能团。还可以应用多官能团和双官能团的混合物,其中多官能团的比例较低。
该具有不稳定氢的官能团可以是醇、伯或仲胺、或硫醇官能团。该化合物可以是在链的末端被具有不稳定氢的这些官能团之一终止的聚合物。
当不涉及聚合物时,顺便提及作为实例的有乙二醇、二甘醇和丙二醇。
当涉及亲水聚合物时,顺便提及作为实例的有聚醚、磺化聚酯、磺化聚酰胺或这些聚合物的混合物。该亲水化合物优选为聚醚,特别是聚环氧乙烷或聚环氧丙烷。
从上述限定的化合物制备的聚合物为按照本发明的两亲阳离子缔合的式I聚合物。该聚合物是水溶性的或水分散性的,可以明显增加其溶解或分散的水溶液的粘度。
在式I中被记为Y的亲水基团是任选的。这是由于具有季铵或质子化胺官能团的单元足可以提供水中的分散度和该类聚合物在水溶液中所必需的溶解度。
尽管亲水基团Y的存在是任选的,然而,两亲阳离子缔合的聚氨酯优选含有这些基团。
由于其良好的增稠性能和其与角蛋白物质极好的亲和性,按照本发明的该类两亲阳离子缔合聚合物特别适合于制备美容用途的局部应用的组合物。
具体地,按照本发明的聚合物可以用于头发组合物,皮肤护理组合物,指甲护理组合物,香水组合物,和用于化妆皮肤、嘴唇、睫毛和指甲的组合物。
式I的两亲阳离子缔合聚合物通过下面的实施例举例说明本发明。
具体实施方式
实施例1:
从下列反应物:
C18H37OH 2mol
亚甲基二环己基二异氰酸酯 4mol
聚乙二醇 1mol
N-甲基乙醇胺 2mol
季铵化剂(CH3)2SO4 2mol
合成平衡离子为CH3SO4 -的下列聚合物:
C18U37-O-CONHR4NHCO-O-(CH2)2-N+(CH3)(CH3)-(CH2)2-O-CONHR2NHCO-O(PEO)O-CONHR2NHCO-O-(CH2)2-N+(CH3)(CH3)-(CH2)2-O-CONHR4NHCO-OC18H37
其中R4=亚甲基二环己基
实施例2:
从下列反应物:
亚甲基二环己基二异氰酸酯 2mol
聚乙二醇 1mol
N,N-二甲基乙醇胺 2mol
季铵化剂C18H37OH 2mol
合成平衡离子为Cl-的下列聚合物:
C18U37N+(CH3)(CH3)-(CH2)2-O-CONHR4NHCO-O(PEO)O-CONHR4NHCO-O(CH2)2-N+(CH3)(CH3)C18H37
其中R4=亚甲基二环己基
实施例3:
反应物:
聚环氧乙烷(PEG)(Mn10000) 0.010mol
亚甲基二环己基二异氰酸酯 0.018mol
N,N-二甲基乙醇胺 0.020mol
硬脂酰溴 0.024mol
辛酸锡(催化剂) 0.2%
将0.010mol(100g)的聚环氧乙烷(PEG)(数均分子量10000)溶解到含有0.2%辛酸锡(催化剂)的105g THF中,然后逐滴加入0.018mol(4.71g)亚甲基二环己基二异氰酸酯。在THF回流下加热反应介质15小时,6小时后加入100ml THF。在反应中,通过FTIR观察到异氰酸酯的NCO带(band)局部消失,出现酰胺键的CO和NH带。该介质非常粘稠并且透明。
随后加入0.020mol(1.78g)的N,N-二甲基乙醇胺,在THF回流下进行反应4小时,直到醇的NCO和OH带完全消失。
为了季铵化,将0.024mol(8g)的硬脂酰溴,也就是说相对于N,N-二甲基乙醇胺过量20%,加入到反应混合物中,然后向非常粘稠的反应介质中加入100g THF。在THF回流下另外加热36小时。
将得到的聚合物从石油醚中沉淀,过滤,在真空、40℃下干燥24小时,得到易碎的的白色粉末。
在水性介质中通过凝胶渗透色谱测定(用聚苯乙烯校准),数均分子量为70000,重均分子量为115000,其对应的多分散指数为1.65。
实施例4:
反应物:
聚(环氧乙烷)(PEG)(Mn10000) 0.010mol
亚甲基二环己基二异氰酸酯 0.020mol
水 0.0334mol
硬脂酰溴 0.022mol
二月桂酸二丁锡(催化剂) 0.5%
在P2O5存在下,将100g聚乙二醇在100℃烘箱中干燥过夜。第二天,应用机械搅拌在100℃下加热PEG,同时用氩气吹扫以除去任何残留痕量的水。反应持续1小时30分钟。随后向PEG中滴加0.53g二月桂酸二丁锡(催化剂)。10分钟后,加入0.020mol(5.24g)亚甲基二环己基二异氰酸酯,反应进行1小时30分钟。加入105g甲苯以减少介质的高粘度。反应22小时后,向反应混合物中加入0.15g亚甲基二环己基二异氰酸酯,进一步反应2小时。
随后加入0.0334mol(6g)的水,反应持续8小时,反应2小时、4小时、6小时后分别分三次加入105g甲苯。反应结束时蒸发掉甲苯。
为了聚合物末端异氰酸酯基团水解得到的伯胺官能团的烷基化,将上述制备的聚合物溶解到105g THF中,以得到50%重量的溶液,加入0.022mol(7.33g)的硬脂酰溴。混合物在THF回流下加热20小时。通过从石油醚中沉淀,过滤,并在40℃真空下干燥24小时,分离得到聚合物。由此得到的是易碎的白色粉末。
在水性介质中通过凝胶渗透色谱(用聚苯乙烯校准)测定的数均分子量为52000,重均分子量为108000,其对应的多分散指数为2.07。
Claims (17)
1.式(I)的水溶性或水分散性的两亲阳离子缔合的聚氨酯:
R-X-(P)n-[L-(Y)m]r-L’-(P’)p-X’-R’ (I)
其中:
R和R’相同或不同,表示疏水基团或氢原子;
X和X’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团或L”基团;
L、L’和L”相同或不同,表示从二异氰酸酯衍生的基团;
P和P’相同或不同,表示含有一个胺基官能团的基团,其可以带有也可以不带有一个疏水基团;
Y表示亲水基团;
r为1-100的整数;
n、m和p具有相互独立的值,在0-1000之间;
该分子含有至少一个质子化的或季铵化的胺官能团和至少一个疏水基团。
2.按照权利要求1的聚氨酯,其特征在于唯一的疏水基团为链末端的R和R’基团。
3.按照权利要求1或2的聚氨酯,其特征在于R和R’独立表示疏水基团,X和X’分别表示L”基团,n和p的值为1-1000,以及L、L’、L”、P、P’、Y和m具有权利要求1所述的含义。
4.按照权利要求1或2的聚氨酯,其特征在于R和R’独立表示疏水基团,X和X’分别表示L”基团,n和p的值为0,以及L、L’、L”、Y和m具有权利要求1所述的含义。
5.按照权利要求1或2的聚氨酯,其特征在于R和R’独立表示疏水基团,X和X’独立表示含有季铵的基团,n和p的值为0,以及L、L’、Y和m具有权利要求1所述的含义。
6.按照权利要求1的聚氨酯,其特征在于r为1-50的整数。
7.按照权利要求1的聚氨酯,其特征在于r为1-25的整数。
8.按照权利要求1或2的聚氨酯,其特征在于其数均分子量在400-500000之间。
9.按照权利要求8的聚氨酯,其特征在于其数均分子量在1000-400000之间。
10.按照权利要求8的聚氨酯,其特征在于其数均分子量在1000-300000之间。
11.按照权利要求1或2的聚氨酯,其特征在于R和R’表示具有饱和或不饱和、直链或支链烃链的基团或聚合物,其中烃链中的一个或多个碳原子可以被选自S、N、O或P的杂原子取代,或被具有硅酮或全氟化链的基团取代。
13.按照权利要求1或2的聚氨酯,其特征在于L、L’和L”相同或不同,表示下式的基团:
其中
Z表示-O-,-S-或-NH-;
以及R4表示具有1-20个碳原子的直链或支链亚烷基,其可以含有也可以不含有饱和或不饱和环,或含有至少一个选自N、S、O或P的杂原子的亚芳基。
15.按照权利要求1或2的聚氨酯,其特征在于Y表示衍生于乙二醇、二甘醇或丙二醇的基团,或衍生于选自聚醚、磺化聚酯和磺化聚酰胺的聚合物的基团。
16.如权利要求1或2所限定的聚氨酯在局部应用化妆用途的组合物中作为增稠剂或胶凝剂的应用。
17.含有化妆品可接受的介质和至少一种如权利要求1或2所限定的聚氨酯的化妆品组合物。
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CN102532459B (zh) * | 2011-11-30 | 2013-09-18 | 烟台万华聚氨酯股份有限公司 | 一种聚氨酯及其制备方法与应用 |
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RU2014147048A (ru) | 2012-04-24 | 2016-06-10 | Л'Ореаль | Способ окрашивания с использованием смеси, включающей загущающий полимер, распыляемой из аэрозольного устройства, и устройство для его осуществления |
EP2841167B1 (en) | 2012-04-24 | 2017-06-14 | L'Oréal | Dyeing process using a mixture obtained from an aerosol device comprising a liquid fatty alcohol and surfactants |
FR2989578A1 (fr) | 2012-04-24 | 2013-10-25 | Oreal | Procede de coloration mettant en oeuvre un melange comprenant un polyol ramifie en c6-c12, obtenu a partir d'un dispositif aerosol et dispositif |
EP2988830B1 (en) | 2013-04-25 | 2021-03-17 | L'Oréal | Composition for straightening keratin fibres, comprising a urea and/or a urea derivative and a nonionic, cationic, amphoteric or anionic associative polymeric thickener, process and use thereof |
FR3044879B1 (fr) | 2015-12-14 | 2018-01-19 | L'oreal | Dispositif de distribution d'un produit de coloration et/ou d'eclaircissement des fibres keratiniques comprenant un polymere associatif |
KR102356559B1 (ko) | 2019-11-25 | 2022-01-27 | 한국생산기술연구원 | 폴리우레탄 필름 형성용 조성물 및 이로부터 유래된 코팅 도막을 포함하는 물품 |
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-
2000
- 2000-07-21 FR FR0009609A patent/FR2811993B1/fr not_active Expired - Fee Related
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2001
- 2001-07-06 EP EP01401818A patent/EP1174450B1/fr not_active Expired - Lifetime
- 2001-07-06 DE DE60144210T patent/DE60144210D1/de not_active Expired - Lifetime
- 2001-07-06 AT AT01401818T patent/ATE501704T1/de not_active IP Right Cessation
- 2001-07-10 PL PL01348571A patent/PL348571A1/xx not_active Application Discontinuation
- 2001-07-16 CN CNB011206128A patent/CN1238391C/zh not_active Expired - Fee Related
- 2001-07-16 US US09/904,516 patent/US20030124079A1/en not_active Abandoned
- 2001-07-16 ZA ZA200105821A patent/ZA200105821B/xx unknown
- 2001-07-17 AR ARP010103400A patent/AR029734A1/es active IP Right Grant
- 2001-07-18 BR BRPI0102946-0A patent/BR0102946B1/pt not_active IP Right Cessation
- 2001-07-18 AU AU54483/01A patent/AU765016B2/en not_active Ceased
- 2001-07-20 HU HU0103041A patent/HUP0103041A3/hu unknown
- 2001-07-20 KR KR10-2001-0043778A patent/KR100437195B1/ko not_active IP Right Cessation
- 2001-07-20 MX MXPA01007393A patent/MXPA01007393A/es not_active Application Discontinuation
- 2001-07-20 CA CA002353342A patent/CA2353342C/fr not_active Expired - Fee Related
- 2001-07-20 RU RU2001120440/04A patent/RU2213102C2/ru not_active IP Right Cessation
- 2001-07-23 JP JP2001221150A patent/JP4212262B2/ja not_active Expired - Fee Related
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2004
- 2004-01-06 US US10/751,514 patent/US20040141943A1/en not_active Abandoned
-
2006
- 2006-01-11 JP JP2006003731A patent/JP2006176789A/ja not_active Abandoned
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2009
- 2009-06-11 US US12/482,769 patent/US20090247650A1/en not_active Abandoned
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HUP0103041A2 (hu) | 2002-04-29 |
JP4212262B2 (ja) | 2009-01-21 |
US20030124079A1 (en) | 2003-07-03 |
DE60144210D1 (de) | 2011-04-28 |
FR2811993A1 (fr) | 2002-01-25 |
AR029734A1 (es) | 2003-07-10 |
BR0102946B1 (pt) | 2009-08-11 |
JP2006176789A (ja) | 2006-07-06 |
ZA200105821B (en) | 2002-02-07 |
CN1334277A (zh) | 2002-02-06 |
US20090247650A1 (en) | 2009-10-01 |
ATE501704T1 (de) | 2011-04-15 |
AU5448301A (en) | 2002-01-24 |
FR2811993B1 (fr) | 2006-08-04 |
BR0102946A (pt) | 2002-03-05 |
EP1174450B1 (fr) | 2011-03-16 |
MXPA01007393A (es) | 2003-05-19 |
PL348571A1 (en) | 2002-01-28 |
AU765016B2 (en) | 2003-09-04 |
CA2353342A1 (fr) | 2002-01-21 |
CA2353342C (fr) | 2006-05-02 |
KR20020008779A (ko) | 2002-01-31 |
RU2213102C2 (ru) | 2003-09-27 |
EP1174450A1 (fr) | 2002-01-23 |
KR100437195B1 (ko) | 2004-06-23 |
US20040141943A1 (en) | 2004-07-22 |
HU0103041D0 (en) | 2001-10-28 |
HUP0103041A3 (en) | 2002-12-28 |
JP2002105161A (ja) | 2002-04-10 |
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