CN100500742C - 制备水包硅油乳液的机械转化方法 - Google Patents
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Abstract
经机械转化来乳化高粘性硅氧烷组合物例如硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂,其中将硅氧烷油包水(W/O)乳液转化为硅氧烷水包油(O/W)乳液。将粘度约十亿厘沲(mm2/s),即1,000,000,000厘沲(mm2/s)的有机硅树脂乳化。这些硅氧烷O/W乳液可用于能够提供提高的美学的个人护理产品。它们也可用于造纸工业和制药工业中用的产品。该硅氧烷O/W乳液比高粘度硅氧烷乳液溶液操作,能够使这些乳液与其它乳液或其它水溶性组分混合。
Description
本发明涉及一种制备含有高粘度硅氧烷的水包硅油乳液的机械转化方法。更具体地说,本发明涉及含有硅橡胶纯胶料、硅橡胶、硅氧烷弹性体、有机硅树脂或其混合物的水包硅油乳液。
硅氧烷乳液在本领域众所周知。这些硅氧烷乳液可以通过例如(i)机械乳化、(ii)经转化的机械乳化或(iii)乳液聚合的方法制得。然而,由于一些硅氧烷例如硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂的粘度高,因此它们的乳化对所有可行的目的都限于乳液聚合。相反,粘度低和因此分子量低的硅氧烷可以容易地机械获得。
然而,使用机械方法来乳化硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂的尝试很难成功,这是由于难以将表面活性剂或表面活性剂的混合物加入到硅橡胶纯胶料、硅橡胶、硅氧烷弹性体或有机硅树脂中。也难以将水加入到含有高粘度硅氧烷、表面活性剂、或表面活性剂的混合物的混合物中,并且同时赋予足够的剪切以引起转化。此外,粒径的控制限制到包括在有溶剂的情况下分批机械乳化的方法。
与上述相反,本发明提供了一种廉价地制备含有具有控制的粒径的硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂的稳定乳液的技术。当它涉及有机硅树脂时它尤其有用,这是由于有机硅树脂用于许多需要水基传输的应用中。
已知MQ型的有机硅树脂和MQ有机硅树脂与硅氧烷聚合物的混合物,当树脂含量高,即以总硅氧烷含量为基础计为20-90%重量时,其乳化难以进行。尽管使用高剪切的直接乳化适用于低粘度混合物,并且通过突发性转化的乳化适用于高粘度混合物,但是二者实际上都不适合存在MQ树脂的情形。这是由于在有机硅树脂/硅氧烷聚合物混合物中存在高水平的硅氧烷MQ树脂大大增加了油相粘度,使得使用高剪切的直接乳化不能得到获得乳液稳定性所需的粒径。此外,大量硅氧烷MQ树脂的存在使得油相抗转化,直至经常油相在任意水油比都保持不转化的程度。
尽管将挥发性硅氧烷流体、挥发性有机流体或低分子量稀释剂与含有高水平的有机硅树脂的油相混合可以使乳化过程容易,但是挥发性和/或低分子量流体和稀释剂的存在在许多应用中可能都不是所需的。
本发明涉及一种制备含有硅橡胶纯胶料、硅橡胶、硅氧烷弹性体、有机硅树脂或其混合物的水包硅油乳液的方法。根据该方法,通过如下制备水包硅油乳液:(i)形成含有硅橡胶纯胶料、硅橡胶、硅氧烷弹性体、有机硅树脂或其混合物的均匀油相;该均匀油相中的硅氧烷具有至少100,000,000(1亿)厘沲(mm2/s)-5,000,000,000(50亿)厘沲(mm2/s)的粘度;(ii)将一种或多种表面活性剂与该均匀油相混合;(iii)向该均匀油相中加入水,形成含有连续相和分散相的油包水乳液,以均匀油相中硅氧烷的重量为基础,水以约0.5-10%重量的量加入;(iv)在长径比(L/D)为至少15的双螺杆挤出机中对该油包水乳液施加高剪切,以引起油包水乳液转化成水包油乳液;和(v)通过加入更多的水将该水包油乳液稀释。
除了(i)中硅橡胶纯胶料、硅橡胶、硅氧烷弹性体或有机硅树脂中存在的溶剂之外,该方法在没有溶剂下进行。均匀油相中的硅氧烷应具有至少100,000,000(1亿)厘沲(mm2/s)-5,000,000,000(50亿)厘沲(mm2/s),优选至少200,000,000(2亿)厘沲(mm2/s)-2,000,000,000(20亿)厘沲(mm2/s)的粘度,并且最优选它应由粘度为至少1,000,000,000(十亿)厘沲(mm2/s)的有机硅树脂构成。
本发明的这些和其它特征在考虑以下的详细描述后将是显而易见的。
说明
本发明提供了一种有效地乳化硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和特别是有机硅树脂的方法。它是通过如下实现的:(i)仅使用非常少量的水,即以油相中硅氧烷的重量为基础计为约0.5-10%重量,优选约1-5%重量,来转化硅油包水(W/O)乳液并形成水包硅油(O/W)乳液;(ii)在转化期间使用长径(L/D)比为至少15,优选至少30,更优选30-60的双螺杆挤出机施加非常高的剪切;和(iii)除了乳化时硅橡胶纯胶料、硅橡胶、硅氧烷弹性体或有机硅树脂中存在的溶剂之外,在没有添加溶剂的情况下进行转化。
该方法特别适合乳化具有至少100,000,000(1亿)厘沲(mm2/s)-5,000,000,000(50亿)厘沲(mm2/s),优选至少200,000,000(2亿)厘沲(mm2/s)-2,000,000,000(20亿)厘沲(mm2/s)的粘度的硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂。这些特征将本发明方法与2003年1月16日申请的题为“有机硅树脂乳液的制备方法”并且受让给与本发明相同受让人的待审美国专利申请序列号10/346.544中所述的方法区别开。
如上所述,本发明涉及硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂。为了本发明的目的,术语硅橡胶和硅氧烷弹性体被认为是同义的,至少一定程度上这两种硅氧烷都能够伸长和复原。相反,硅橡胶纯胶料可以被拉伸,但是通常不能迅速回复。硅橡胶纯胶料是高分子量通常线性的聚二有机基硅氧烷,它可以由其高粘性塑料状态通过交联转变成主要弹性的状态。硅橡胶纯胶料经常用作制备硅氧烷弹性体和硅橡胶的一种主要成分。
为了本发明的目的,可以认为硅橡胶纯胶料包括美国专利3,692,737(1972年9月19日)、美国专利4,152,416(1979年5月1日)、美国专利4,885,129(1989年8月8日)和美国专利5,057,240(1991年10月15日)中所述类型的组合物,感兴趣的读者可以参考。
可以认为硅橡胶和硅氧烷弹性体包括美国专利4,882,377(1989年11月21日)、美国专利5,654,362(1997年8月5日)、美国专利5,994,459(1999年10月30日)和美国专利6,015,858(2000年1月18日)中所述类型的组合物,感兴趣的读者可以参考。
可以认为有机硅树脂包括美国专利2,676,182(1954年4月20日)、美国专利4,310,678(1982年1月12日)、美国专利4,423,095(1983年12月27日)和美国专利5,356,585(1994年10月18日)中所述类型的组合物,感兴趣的读者可以参考,以及下面更详细描述的组合物。
涉及有机硅树脂的缩写词MQ得自符号M、D、T和Q,它们各自代表可以存在于含有通过≡Si-O-Si≡键连接的硅氧烷单元的硅氧烷中的不同类型结构单元的官能度。单官能的(M)单元代表(CH3)3SiO1/2,二官能的(D)单元代表(CH3)2SiO2/2。三官能的(T)单元代表CH3SiO3/2,并且使得形成支化的线性硅氧烷。四官能的(Q)单元代表SiO4/2,它使得形成交联和树脂状的硅氧烷组合物。因此当硅氧烷含有所有的单官能的M和四官能的Q单元,或者至少含有高百分数的M和Q单元例如使得硅氧烷为树脂状时,采用MQ。
本文所用的有机硅树脂是玻璃化转变温度(Tg)大于0℃的非线性有机硅树脂。玻璃化转变温度是无定形材料例如高级硅氧烷聚合物从易碎的玻璃态变为塑性状态的温度。有机硅树脂通常具有式R′aSiO(4-a)/2,其中R′是具有1-6个碳原子的一价烃基或具有1-6个碳原子的官能取代的烃基,a具有1-1.8的平均值。有机硅树脂将优选由单官能的(M)单元R"3SiO1/2和四官能的(Q)单元SiO4/2组成,其中R"是具有1-6个碳原子的一价烃基,最优选甲基。通常,M基团与Q基团的数量比将在0.5:1-1.2:1的范围内,以提供其中式R′aSiO(4-a)/2中的a具有1.0-1.63的平均值的当量。优选,该数量比是0.6:1-0.9:1。最优选每个分子中Q单元的数量高于1,优选高于5的硅氧烷MQ树脂。
有机硅树脂也可以含有1-5%重量的与硅键合的羟基例如二甲基羟基甲硅烷氧基单元(HO)(CH3)2SiO1/2。如果需要的话,有机硅树脂可以含有少量的二官能的(D)单元和/或三官能的(T)单元。优选的有机硅树脂是粘度为至少100,000,000(1亿)厘沲(mm2/s)并且软化温度低于约200℃的那些。有机硅树脂可以由如下组成:(i)MxQy型的有机硅树脂,其中x和y具有使得有机硅树脂每个分子含有至少大于5个Q单元的值;(ii)MxTy型的有机硅树脂,其中x和y具有使得有机硅树脂每个分子含有至少大于5个T单元的值;和(iii)MxDyTpQq型的有机硅树脂,其中x、y、p和q具有使得每个分子中Q和T单元的总数是至少大于5个单元并且D单元的数量在0-100变化的值。
使用表面活性剂制备本发明的乳液。表面活性剂可以是阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂、或者表面活性剂的混合物。优选非离子表面活性剂和阴离子表面活性剂,最优选含有阴离子和非离子表面活性剂的混合物、或者含有两种非离子表面活性剂的混合物。当使用含有非离子表面活性剂的混合物时,一种非离子表面活性剂应具有低的亲水-亲脂平衡(HLB),并且另一非离子表面活性剂应具有高的HLB,使得两种非离子表面活性剂具有11-15的组合HLB,优选12.5-14。5的组合HLB。
适宜的阴离子表面活性剂的代表性实例包括高级脂肪酸的碱金属皂、烷基芳基磺酸盐例如十二烷基苯磺酸钠、长链脂肪醇磺酸盐、烯烃硫酸盐和烯烃磺酸盐、硫化单甘油酯类、硫化酯类、磺化乙氧基化醇类、磺基丁二酸盐、链烷磺酸盐、磷酸酯类、烷基羟乙磺酸盐、烷基牛磺酸盐和烷基肌氨酸盐。优选的阴离子表面活性剂的一个实例是工业上以名称Bio-Soft N-300销售的。它是由Stephan Company,Northfield,Illinois销售的三乙醇胺线性烷基化物磺酸盐组合物。
适宜的阳离子表面活性剂的代表性实例包括烷基胺盐、季铵盐、锍盐和鏻盐。适宜的非离子表面活性剂的代表性实例包括环氧乙烷与长链脂肪醇或脂肪酸例如C12-16醇的缩合物、环氧乙烷与胺或酰胺的缩合物、乙烯和环氧丙烷的缩合产物、甘油酯、蔗糖、山梨糖醇、脂肪酸烷醇酰胺、蔗糖酯、氟-表面活性剂和脂肪胺氧化物。适宜的两性表面活性剂的代表性实例包括咪唑啉化合物、烷基氨基酸盐和甜菜碱。
适宜的可商购获得的非离子表面活性剂的代表性实例包括以商标名BRIJ由Uniqema(ICI Surfactants),Wilmington,Delaware销售的聚氧乙烯脂肪醇。一些实例是BRIJ 35 Liquid,一种已知为聚氧乙烯(23)月桂基醚的乙氧基化醇,和BRIJ 30,另一种已知为聚氧乙烯(4)月桂基醚的乙氧基化醇。一些其它的非离子表面活性剂包括以商标由Dow Chemical Company,Midland,Michigan销售的乙氧基化醇类。一些实例是 TMN-6,一种已知为乙氧基化三甲基壬醇的乙氧基化醇;和各种乙氧基化醇类,即C12-C14仲醇乙氧基化物,以商标 15-S-5、 15-S-12、15-S-15和 15-S-40销售。也可以使用含有硅原子的表面活性剂。
相转化通常发生在连续相的分散体变成分散相的时候,或者反之亦然。液/液分散体的相转化被分类成突发性转化或过渡转化。突发性转化是通过简单变化相比例直到分散相的比例足够高至它变成连续相而引起的。过渡转化发生在改变表面活性剂对两相的亲和力以便引起转化的时候。本发明发生的转化是突发性的转化。
因此,本发明用于制备硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和有机硅树脂乳液的转化方法是通过如下进行的:(i)形成含有硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和/或有机硅树脂的油相;(i)将该油相在双螺杆挤出机中混合并搅拌;(iii)向含有硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和/或有机硅树脂的油相中加入表面活性剂;和(iv)在双螺杆挤出机中对该油相进行搅拌和混合。在步骤(v)中,以逐步方式向含有表面活性剂、硅橡胶纯胶料、硅橡胶、硅氧烷弹性体和/或有机硅树脂的油相中加入有限和非常少量的水,使得发生突发性转化,并形成水包油乳液。
通常,以油相中存在的硅氧烷的重量为基础,步骤(v)中所需的水量是约0.5-10%重量。优选,以油相中存在的硅氧烷的重量为基础,水量将是约1-5%重量。尽管可以分2-4份加入水,但优选以单份加入水。水的最初添加可以包括表面活性剂。在获得所需的粒径之后,用平衡的水将乳液稀释以获得优选的固体含量。
需要双螺杆挤出机中的高剪切来诱导该转化。双螺杆挤出机应具有至少15,优选至少30,更优选30-60的长径(L/D)比。如果需要的话,也可以使用具有带挤出螺杆的双臂混合器的捏合挤出机来诱导转化,前提是捏合挤出机能够起与双螺杆挤出机的相同效率的作用。乳液在形成最终组合物时可以含有其它添加剂例如杀生物剂、增稠剂和冻-融稳定剂。乳液中硅氧烷的粒径通常在约0.1-25.0微米的范围内,这取决于制备中使用的表面活性剂和硅氧烷的量和特性。
期望本发明的方法能够形成硅橡胶纯胶料、硅橡胶、硅氧烷弹性体、有机硅树脂及其混合物的O/W乳液,其中硅氧烷具有至少100,000,000(1亿)厘沲(mm2/s)-5,000,000,000(50亿)厘沲(mm2/s)的粘度。优选,硅氧烷组分应具有至少200,000,000(2亿)厘沲(mm2/s)-2,000,000,000(20亿)厘沲(mm2/s)的粘度。还期望该方法可以在不添加除了乳化时硅橡胶纯胶料、硅橡胶、硅氧烷弹性体或有机硅树脂中存在的溶剂之外的溶剂的情况下进行。本发明的乳化方法能够没有障碍地将活性成分引入到水或油相中。
本发明的硅氧烷O/W乳液能够传输性能特征例如受控的粘性和润滑性,并且有助于成膜。它们可用于涂布应用、家庭、化妆和个人护理应用,从而提供较大的耐用性、保护质量、防水性和阻挡性能。用于个人护理产品的硅氧烷O/W乳液能够提供良好的美学。它们也可用于打算用于纸和制药工业的产品中。由于硅氧烷O/W乳液比高粘度硅氧烷易于操作,因此它们便于与其它乳液或水溶性组分混合。
下面的实施例更详细地描述本发明。在这些实施例中,双螺杆挤出机具有与美国专利5,354,804(1994年10月11日)中所示的双螺杆挤出机相似的结构,感兴趣的读者可以参考。它具有约56英寸(1,400毫米)的长度,并且含有一对直径各自为约1英寸(25毫米)的螺杆。然而,本领域已知的任意双螺杆挤出机都适宜进行该方法。例如,双螺杆挤出机可以反转和共转。它可以配备有圆锥形双螺杆或者平行双螺杆。双螺杆挤出机的筒可以分成多个区域,并且沿筒的长度配备有加入材料用的计量设备。
实施例1:含有硅橡胶纯胶料的乳液
通过将粘度为约100,000,000厘沲(mm2/s)的硅橡胶纯胶料泵送到双螺杆挤出机中而将该高粘度硅橡胶纯胶料乳化。该硅橡胶纯胶料是含有约0.14%的苯基甲基硅氧烷单元的二甲基乙烯基甲硅烷氧基封端的聚二甲基硅氧烷。以American Society for Testing and Materials(ASTM)Test Procedure D-926中所述的测定方案为基础,它呈现约55-65密耳的可塑度。将Tergitol 15-S-5和Tergitol 15-S-40非离子表面活性剂加入到该硅橡胶纯胶料中并混合。将少量的水(水1)加入到该预混物中,并将该预混物中的组分混合直至发生转化并获得适当的粒径。在双螺杆挤出机的出口端用水(水2)稀释所得超高固体硅氧烷O/W乳液来调整它的固体含量。该方法参数示于表1。表1中的断面(section)数值是指沿配备有能够加入材料的入口的双螺杆挤出机的筒体的长度的加入点。这些断面还通过距离双螺杆挤出机的入口端的距离(以毫米计)标识。试验2(星号表示)中的水1是在断面4在350mm加入的,而不是在断面3加入。
表1
组分 | 加入点 | 试验1 | 试验2 |
硅橡胶纯胶料,g/min | 断面1-50mm | 150 | 250 |
Tergitol 15-S-40,g/min,非离子 | 断面2-150mm | 6.0 | 11.2 |
Tergitol 15-S-5,g/min,非离子 | 断面2-150mm | 2.0 | 3.84 |
水1,g/min | 断面3-250mm | 3.8 | 12.4* |
水2,g/min | 断面10-950mm | 18.8 | 26.3 |
总量,g/min | 180.6 | 303.7 | |
水速1,Wt.% H<sub>2</sub>O/Wt.%预混物 | 2.4 | 4.7 | |
水速2,Wt.% H<sub>2</sub>O/Wt.%预混物 | 11.9 | 9.9 | |
螺杆速度,rpm | 608 | 198 | |
固体重量百分比 | 87.0 | 87.3 | |
粒径,μm | 23.4 | 27.9 |
实施例2:含有有机硅树脂的乳液
通过将粘度为约十亿厘沲(mm2/s),即1,000,000,000厘沲(mm2/s)的有机硅树脂泵送到双螺杆挤出机中而将该高粘度有机硅树脂乳化。该有机硅树脂是70重量%的基本上由单官能的(CH3)3SiO1/2M单元和四官能的SiO4/2Q单元组成的有机硅树脂共聚物的二甲苯溶液的形式。MQ单元以约0.75:1的摩尔比存在于有机硅树脂中。以固体的重量为基础,有机硅树脂含有约2.4-2.9重量%的羟基官能度。它是按照American Society for Testing and Materials(ASTM)TestProcedure E-168中所述的测定方案通过傅立叶变换红外光谱(FTIR)分析测定的。将该双螺杆挤出机加热至60℃。将Brij 30非离子表面活性剂和Bio-Soft N-300阴离子表面活性剂加入到该有机硅树脂中并混合。将少量的水(水1)加入到该预混物中,并将该预混物混合直至发生转化并获得适当的粒径。在双螺杆挤出机的出口端用水(水2)稀释所得超高固体硅氧烷O/W乳液来调整它的固体含量。该方法参数示于表2。表2中的断面数值是指沿配备有能够加入材料的入口的双螺杆挤出机的筒体的长度的加入点。
表2
组分 | 加入点 | 试验1 | 试验2 |
有机硅树脂,g/min | 断面1-50mm | 103.4 | 102.4 |
Brij 30,g/min,非离子 | 断面2-150mm | 6.8 | 4.8 |
Bio-Soft N-300,g/min,阴离子 | 断面3-250mm | 6.0 | 4.3 |
水1,g/min | 断面4-350mm | 5.0 | 5.0 |
水2,g/min | 断面12-1150mm | 19.6 | 19.6 |
总量,g/min | 140.8 | 136.1 | |
水速1,Wt.% H<sub>2</sub>O/Wt.%预混物 | 4.3 | 4.5 | |
水速2,Wt.% H<sub>2</sub>O/Wt.%预混物 | 16.9 | 17.6 | |
螺杆速度,rpm | 317 | 317 | |
固体重量百分比 | 82.6 | 81.9 | |
粒径,μm | 0.34 | 0.36 |
实施例3:含有硅氧烷弹性体的乳液
通过将按照美国专利5,654,362(1997年8月5日)中所述的方法制备的硅氧烷弹性体泵送到双螺杆挤出机中而将该硅氧烷弹性体乳化。将该双螺杆挤出机加热到30℃。将Tergitol 15-S-12非离子表面活性剂加入到该硅氧烷弹性体中并混合。将少量的水(水1)加入到该预混物中,并将该预混物混合直至发生转化并获得适当的粒径。在双螺杆挤出机的出口端用水(水2)稀释所得硅氧烷O/W乳液来调整它的固体含量。该方法参数示于表3。表3中的断面数值是指沿配备有能够加入材料的入口的双螺杆挤出机的筒体的长度的加入点。
表3
组分 | 加入点 | 试验1 | 试验2 |
硅氧烷弹性体,g/min | 断面1-50mm | 218.0 | 350.0 |
Tergitol 15-S-12,g/min,非离子 | 断面2-150mm | 5.4 | 8.2 |
水1,g/min | 断面3-250mm | 3.7 | 4.0 |
水2,g/min | 断面12-1150mm | 19.6 | 43.8 |
总量,g/min | 246.7 | 406.0 | |
水速1,Wt.% H<sub>2</sub>O/Wt.%预混物 | 1.7 | 1.12 | |
水速2,Wt.% H<sub>2</sub>O/Wt.%预混物 | 8.8 | 12.2 | |
螺杆速度,rpm | 1200 | 1200 | |
固体重量百分比 | 90.6 | 88.2 | |
粒径,μm | 17.4 | 23.7 |
在不背离本发明的主要特征的情况下可以对本文所述的化合物、组成和方法进行其它改变。本文具体所述的本发明的实施方式仅是例证的,不打算限制其范围,其范围仅由附加的权利要求书定义。
Claims (7)
1、一种制备水包硅油乳液的方法,包括步骤:(i)形成含有硅橡胶纯胶料、硅氧烷弹性体、有机硅树脂或其混合物的均匀油相;该均匀油相中的硅氧烷具有至少100,000,000厘沲至5,000,000,000厘沲的粘度;(ii)将一种或多种表面活性剂与该均匀油相混合;(iii)向该均匀油相中加入水,形成含有连续相和分散相的油包水乳液,以均匀油相中硅氧烷的重量为基础,水以0.5-10%重量的量加入;(iv)在长径L/D比为至少15的双螺杆挤出机中对该油包水乳液施加高剪切,以引起油包水乳液转化成水包油乳液;和(v)通过加入水将该水包油乳液稀释;除了(i)中硅橡胶纯胶料、硅氧烷弹性体或有机硅树脂中存在的溶剂之外该方法在没有溶剂的情况下进行。
2、权利要求1的方法,其中均匀油相中的硅氧烷具有至少200,000,000厘沲至2,000,000,000厘沲的粘度。
3、权利要求1的方法,其中均匀油相中的硅氧烷具有至少1,000,000,000厘沲的粘度。
4、权利要求1的方法,其中均匀油相中的硅氧烷是有机硅树脂。
5、权利要求1的方法,其中以均匀油相中的硅氧烷的重量为基础,(iii)中水的加入量是1-5%重量。
6、权利要求1的方法,其中双螺杆挤出机的L/D比是15-60。
7、一种根据权利要求1所述的方法制备的水包硅油乳液。
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- 2004-04-19 AT AT04801849T patent/ATE466911T1/de not_active IP Right Cessation
- 2004-04-19 JP JP2006521051A patent/JP4857109B2/ja not_active Expired - Lifetime
- 2004-04-19 US US10/559,525 patent/US7385001B2/en active Active
- 2004-04-19 CN CNB2004800195358A patent/CN100500742C/zh not_active Expired - Fee Related
- 2004-04-19 DE DE602004027047T patent/DE602004027047D1/de not_active Expired - Lifetime
- 2004-04-19 WO PCT/US2004/012001 patent/WO2005016998A2/en active Application Filing
- 2004-04-19 EP EP04801849A patent/EP1646696B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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WO2005016998A3 (en) | 2005-04-21 |
CN1820041A (zh) | 2006-08-16 |
ATE466911T1 (de) | 2010-05-15 |
US20060135626A1 (en) | 2006-06-22 |
TW200504124A (en) | 2005-02-01 |
US7385001B2 (en) | 2008-06-10 |
DE602004027047D1 (de) | 2010-06-17 |
WO2005016998A2 (en) | 2005-02-24 |
EP1646696B1 (en) | 2010-05-05 |
JP2006528714A (ja) | 2006-12-21 |
EP1646696A2 (en) | 2006-04-19 |
TWI335923B (en) | 2011-01-11 |
JP4857109B2 (ja) | 2012-01-18 |
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