CN1286910C - 含聚酯组合物的型坯和瓶制品及该型坯的制法 - Google Patents
含聚酯组合物的型坯和瓶制品及该型坯的制法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
本发明涉及选自型坯或瓶的产品，该产品含有一种聚酯组合物与大约5至50ppm(基于所述热塑性聚合物的量计算)的氧化铁黑粒子，所述组合物具有较大的再热速率改进百分数(RIV)与仅仅在透明度(ΔL★)上很小的降低的有利的结合。所述RIV/ΔL★的比例高于大约2.0，其中所述RIV和ΔL★是根据除不存在氧化铁外其余均相同的组合物测定的。本发明还涉及一种包括从聚酯组合物形成型坯的方法。
Description
本发明专利申请是中国专利申请号为99802248.9、申请日为1999年1月19日、发明名称为《(含氧化铁黑的热塑性聚合物组合物》的中国专利申请的分案申请。
本专利申请要求1998年1月23日递交的美国临时专利申请序列号60/072,365的权益。
技术领域
本发明涉及改进再热性的透明、无色热塑性聚合物的生产。本发明在饮料瓶生产领域中有特别的用处。
背景技术
用于工业生产饮料瓶的聚合物料坯(型坯)再热所用的加热灯通常为石英灯，这种石英灯具有从500nm到高于1500nm的宽的光发射光谱。石英灯的最大光发射存在于大约1100-1200nm的范围内。聚酯特别是聚对苯二甲酸乙二醇酯(“PET”)在500至1400nm的区域内基本不吸收。因此为了加速瓶生产中的再热步骤，可将在700-1200nm范围内吸收光的试剂加入到所述聚酯聚合物中。
以前人们将各种黑色和灰色体吸收化合物用作再热试剂以改进聚酯在石英灯下的升温特性。然而，这些化合物赋颜色予聚合物。因此能被加入到聚合物中的吸收化合物的量因其影响所述聚合物的视觉性质(如透明性)而受到限制。透明性在加德纳色系中以“L★”表示，L★为100表示100％的透明和L★为0表示100％的不透明。通常，深颜色再热试剂由于它们对L★的不利影响仅能以非常少的量加入。
以前公开的有用的聚合物再热试剂的例子包括炭黑(美国4,408,004)和还原锑金属(美国5,419,936和美国5,529,744)。另外美国4,420,581和美国4,250,078公开了在含有绿色染料的聚酯中使用氧化铁红作为红外吸收剂。由于所述绿色染料掩盖了红色色调，因此所述氧化铁红加入的红色色调在使用上不会有什么问题。然而人们发现无色和绿色饮料瓶是有商业用处的，所以红色色调的瓶子没有销路。如果不掩盖绿色染料的存在，氧化铁红将给其它无色的、或中性色彩的聚酯瓶带来不符合需要的红色色彩。
更深颜色的吸收化合物通常比相对浅的吸收化合物更好地改进升温特性。然而，所述更深颜色吸收化合物由于对于L★的更大的不利影响而仅能以非常少的量加入。例如，当炭黑(非常深黑色的化合物)以高于几个ppm的浓度加入PET中时，由该PET生产的吹塑瓶在外观上已是很灰且暗。还原锑金属能以多至大约50ppm的浓度存在于PET中而没有对L★产生过度的不利影响，这是因为还原锑金属是灰色金属，其在颜色上比纯黑色体吸收剂(如炭黑)浅得多。
美国专利4,481,314公开了作为改进再热速率的目的而使用某些蒽醌类染料。然而，这些染料基本上是在可见光谱内吸收，导致了所述聚合物的着色。另外，它们相对低的摩尔吸光系数(ε)(在20,000的范围内)要求在聚合物中使用相对大量的这类染料(20-100ppm)。在浓度为50ppm时，所述再热速率改进7％。然而，在这些水平上，所述聚合物显示出淡绿色，这不适合于生产透明、中性色彩的瓶子。
根据上述观点，希望得到一种红外吸收物质，其可以以足以有效提高所述热塑性聚合物大约10％的所述再热速率的浓度加入到该聚合物中，而对于聚合物L★的有害影响不象以前所知的有效的聚合物再热试剂那样大。
发明内容
本发明是热塑性聚合物组合物，其含有与大约5至50ppm(基于所述热塑性聚合物的量计算)的氧化铁黑颗粒掺和的热塑性聚合物的共混物。
本申请人发现当将氧化铁黑(Fe3O4)在相对高的浓度(多至大约50ppm)下使用时它是非常有效的聚酯再热试剂。使用50ppm的氧化铁黑时所述聚合物再热速率的提高是与加入仅为大约5ppm的氧化铁黑时提供的聚合物再热速率的提高相比较的。本申请人发现尽管事实上为了在再热速率上得到同样的提高，必须在聚合物中掺和更高浓度的氧化铁黑，然而所述在再热速率上的提高是在使用氧化铁黑而对于聚合物L★较小的有害影响的情况下得到的。
本发明的另外的好处是不象其它的黑色或灰色体吸收化合物，氧化铁黑由于铁的可检测性而在生成的聚酯组合物中可容易地定量检测。由于炭黑和锑金属不能够被定量地与聚酯中固有的其它形式的碳和锑相区别，因而这为在处理和生产中控制与聚合物掺和的吸收试剂的量提供了极大的改进。
本发明是热塑性聚合物组合物，其含有与从大约5至50ppm(基于所述聚合物的量计算)的氧化铁黑(Fe3O4)掺和的热塑性聚合物共混物。由本发明组合物形成的制品(如饮料瓶)将显示出L★仅仅稍低于(较低的透明度)由所述同样的聚合物而不存在所述氧化铁黑形成的制品的L★。本发明聚合物组合物具有改进的(较少的)再热时间，在石英灯下至多达大约15％。
当与除了不存在氧化铁外其它均一样的组合物相比较时，本发明的热塑性聚合物组合物的再热速率改进与透明性变化的比(RIV/ΔL★)具有意想不到的高比率。所述再热改进(RIV)百分比是所述聚合物掺和有氧化铁黑后聚合物再热速率的改进。ΔL★是所述氧化铁黑与聚合物掺和后在所述聚合物的透明度上的改变量。本发明的组合物的RIV与ΔL★的比优选高于大约2.0，更优选高于大约2.5。作为比较，与炭黑掺和的热塑性聚合物的RIV与ΔL★的比为大约1.5。因此，本发明的组合物的RIV与ΔL★的比优于具有相似的RIV的炭黑聚合物组合物的RIV与ΔL★的比。
本发明的所述组合物优选通过将氧化铁黑颗粒在聚合过程中或其后掺和到所述聚合物反应体系中、掺和到聚合物熔体中或掺和到形成所述瓶子型坯的模塑粉料或粒料中得到。为了得到充分的混合，应该将所述氧化铁黑在所述聚合物的固有粘度(I.V.)为大约0.6至0.8dL/g(在25℃下、于苯酚/四氯乙烷为60/40wt/wt中测定)时加入。
本发明聚合物组合物中的氧化铁黑的适合浓度在大约5至50ppm之间，优选在大约7至30ppm之间，更优选大约10至20ppm的浓度。所述氧化铁黑的浓度是基于所述组合物中的聚合物的量计算的。
在本发明中使用的氧化铁黑的平均粒径优选在大约0.1至10μm(微米)之间，更优选在大约0.5至5μm之间。更大的颗粒的存在将导致由所述聚合物组合物形成的瓶子变得雾化。
在本发明组合物中的热塑性聚合物可以是任何结晶的热塑性均聚物或共聚物。然而，在本发明中使用的热塑性聚合物最有用的是聚酯，尤其是部分芳族聚酯，特别是至少主要是由芳族二酸和脂族二醇衍生的聚酯。优选的聚酯是含有至少70％(mol)、优选70％至100％(mol)、更优选至少85％(mol)的对苯二甲酸乙二醇酯单元的聚酯。
除由对苯二甲酸衍生的单元外，本发明聚酯中的酸成分可用从一种或多种其它的二羧酸衍生的单元改性。这些其它的二羧酸包括：芳族二羧酸(优选含有8至14个碳原子)、脂族二羧酸(优选含有4至12个碳原子)或脂环族二羧酸(优选含有8至12个碳原子)。能用于改性所述酸成分的二羧酸单元的例子如从苯二甲酸、间苯二甲酸、萘-2，6-二甲酸、环己二甲酸、环己二乙酸、二苯基-4，4’-二酸、丁二酸、戊二酸、己二酸、壬二酸和癸二酸等衍生得到的单元，最优选间苯二甲酸、萘-2，6-二甲酸和环己二甲酸。应该理解使用这些酸相应的酸酐、酯和酰基氯是包含在术语“二羧酸”中的。
除由乙二醇衍生的单元外，本发明聚酯的二醇成分可用由其它二醇得到的单元改性，所述其它的二醇包括：脂环族二醇(优选含有6至20个碳原子)和脂族二醇(优选含有3至20个碳原子)。这些二醇的例子包括：二甘醇、三甘醇、1，4-环己二甲醇、丙-1，3-二醇、丁-1，4-二醇、戊-1，5-二醇、己-1，6-二醇、3-甲基戊二醇-(2，4)、2-甲基戊二醇-(1，4)、2，2，4-三甲基戊-二醇-(1，3)、2-乙基己二醇-(1，3)、2，2-二乙基丙-二醇-(1，3)、己二醇-(1，3)、1，4-二(羟基乙氧基)-苯、2，2-二-(4-羟基环己基)-丙烷、2，4-二羟基-1，1，3，3-四甲基-环丁烷、2，2-二-(3-羟基乙氧基苯基)-丙烷和2，2-二-(4-羟基丙氧基苯基)-丙烷。
本发明的聚合物可通过本领域熟知的常规的聚合方法制备。聚酯的缩聚方法包括二羧酸和二醇的直接缩合、酯交换和固相聚合方法。通常可被使用的聚酯化催化剂包括钛的醇盐、二月桂酸二丁基锡和氧化锑或三乙酸锑，可分开或结合使用，任选含有锌、锰或镁的乙酸盐或苯甲酸盐和/或其它为本领域的技术人员所熟知的此类催化剂物质。磷和钴的化合物也作为任选存在。
可将其它成分加入本发明的组合物中以增强所述聚酯组合物的工作特性。例如结晶助剂、冲击改性剂、表面润滑剂、不套叠剂(denesting agents)、稳定剂、抗氧化剂、紫外光吸收剂、金属减活剂、着色剂、成核剂、乙醛还原化合物、其它再热还原助剂、填料等均可包括在内。所述树脂还可含有少量的支化剂如三官能或四官能共聚单体例如1，2，4-苯三酸酐、三羟甲基丙烷、1，2，4，5-苯四酸二酐、季戊四醇和其它本领域通常所知的聚酯形成的多酸或多羟基化合物。所有的这些和许多其它添加剂及它们的使用是本领域所熟知的，不需要展开讨论。任何这些化合物可在本发明组合物中使用只要它们不阻碍本发明完成它的目的即可。因此，优选本发明组合物主要由热塑性聚合物和氧化铁黑的共混物组成，并仅存在改性量的其它成分。
可将本发明的聚合物组合物用于形成瓶子型坯，也已知为料坯，其为试管形状的注塑物品。通常通过使型坯通过一排石英红外加热灯的前面、将所述型坯放置于瓶的模具中并从模具的开口端吹入压缩空气而将所述型坯加热到高于所述聚合物组合物的玻璃化转变温度大约10℃。
具体实施方式
本发明涉及以下具体实施方案：
实施方案1.一种选自型坯或瓶的制品，该制品含有一种聚酯组合物，其特征在于该聚酯组合物含有一种聚酯聚合物与基于所述的聚酯聚合物量计算的5至50ppm的氧化铁黑颗粒，其中所述组合物具有的再热速率改进百分数与透明度变化的比(RIV/ΔL★)高于2.0，其中所述RIV和ΔL★是根据除不存在氧化铁外其余均相同的组合物测定的。
实施方案2.实施方案1的制品，其中氧化铁黑的浓度为7至30ppm。
实施方案3.实施方案1的制品，其中所述颗粒具有0.1至10μm的粒径。
实施方案4.实施方案1的制品，其中所述聚酯含有70至100％mol的从对苯二甲酸乙二醇酯得到的重复单元。
实施方案5.一种制备透明成品的方法，包括由聚酯组合物形成型坯，该聚酯组合物含有一种聚酯聚合物与基于所述聚酯聚合物的量计算的5至50ppm的氧化铁黑颗粒，其中所述组合物具有的再热速率改进百分数与透明度变化的比(RIV/ΔL★)高于2.0，其中所述RIV和ΔL★是根据除不存在氧化铁外其余均相同的组合物测定的；在石英灯下再热所述型坯至适合吹塑的温度并将所述型坯吹塑得到透明成品的步骤。
实施方案6.实施方案5的方法，其中氧化铁黑的浓度为7至30ppm。
实施方案7.实施方案5的方法，其中所述颗粒还具有0.1至10μm的粒径。
实施方案8.实施方案5的方法，其中所述聚酯含有70至100％mol的从对苯二甲酸乙二醇酯得到的重复单元。
本发明通过以下实施例作说明。然而，这些实施例不应解释为是对本发明的限定。
实施例
制备含有不同水平的氧化铁黑(BI0)和炭黑(CB)的聚苯二甲酸乙二醇酯(PET)聚合物组合物。所述聚合物的相对再热速率采用以下方法测定：
将所述聚合物样品注塑进3”×3”×0.150”的平面瓷花金属板中。将所述瓷化金属板放置24hrs以降至室温。将一组四个作为对比的标准瓷化金属板和每个样品四个瓷化金属板采用以下方法处理。
将瓷化金属板放置于木架上，该木架仅仅与所述瓷化金属板的边沿接触。测量在木架上的所述瓷化金属板的温度。这就是所述初始温度(Ti)。将所述架子移至钨石英加热灯(与那些在再热吹塑机中使用的相同)前固定距离的位置。调节所述灯使其在温度为华氏4,000度(λ★ max大约为1,100nm)下发光。所述灯的打开时间为35秒。然后通过红外高温计读出所述瓷化金属板的温度。所述温度是从所述瓷花金属板的未被照射的那一面读出的。这样做是使得由所述瓷化金属板前面的一面吸收的热可以渗透过所述瓷化金属板。所述瓷化金属板的背面的温度一开始升至一最高温度，然后在整个瓷化金属板冷却时慢慢回落。所述最高温度记录为最终温度(Tf)。
所述温度的升高记录为ΔT(Tf-Ti)。温度的变化也因所述瓷化金属板在厚度上的微小差别而作调整。然后将所述四个瓷化金属板调整后的ΔT作平均得到每个样品的ΔTavg。每个样品的ΔTavg被平行实验的作为参比标准的ΔT所除，以得到所述再热指数值(RIV)＝(ΔTavg样品÷ΔTave参比)。
再热改进百分数按下式计算：
再热改进％＝((RIV样品-RIV对照)÷RIV时照)×100下表1显示在相等的再热改进(RIV)上，与所述炭黑(CB)样品相比，所述氧化铁黑(BIO)样品显示出较好的L★。这个性质在以下以RIV/ΔL★定量。
表1
| 添加剂 | 浓度(ppm) | RIV | L★ | ΔL★ | RIV/ΔL★ |
| BIO对照BIO对照BIOBIOBIOCB对照CB对照CBCBCBCBSb金属 | 00258000.5124？ | 0.00％0.00％0.29％3.17％6.35％0.00％0.00％2.85％5.72％10.07％19.40％ | 86.3085.8185.7884.5483.0986.6086.4484.0782.1879.5673.3783.44 | 0.00-0.03-1.27-2.720.00-2.37-4.26-6.88-13.07 | 9.672.502.331.201.341.461.48 |
将表1得到的数据以再热添加剂的浓度与预测在更高和更低的浓度下的性能为函数作图，测定所述氧化铁黑在所述组合物中的浓度限定范围，其在本发明中在大约5至50ppm之间。
Claims (8)
1.一种选自型坯或瓶的制品，该制品含有一种聚酯组合物，其特征在于该聚酯组合物含有一种聚酯聚合物与基于所述的聚酯聚合物量计算的5至50ppm的氧化铁黑颗粒，其中所述组合物具有的再热速率改进百分数与透明度变化的比(RIV/ΔL★)高于2.0，其中所述RIV和ΔL★是根据除不存在氧化铁外其余均相同的组合物测定的。
2.权利要求1的制品，其中氧化铁黑的浓度为7至30ppm。
3.权利要求1的制品，其中所述颗粒具有0.1至10μm的粒径。
4.权利要求1的制品，其中所述聚酯含有70至100％mol的从对苯二甲酸乙二醇酯得到的重复单元。
5.一种制备透明成品的方法，包括由聚酯组合物形成型坯，该聚酯组合物含有一种聚酯聚合物与基于所述聚酯聚合物的量计算的5至50ppm的氧化铁黑颗粒，其中所述组合物具有的再热速率改进百分数与透明度变化的比(RIV/ΔL★)高于2.0，其中所述RIV和ΔL★是根据除不存在氧化铁外其余均相同的组合物测定的；在石英灯下再热所述型坯至适合吹塑的温度并将所述型坯吹塑得到透明成品的步骤。
6.权利要求5的方法，其中氧化铁黑的浓度为7至30ppm。
7.权利要求5的方法，其中所述颗粒还具有0.1至10μm的粒径。
8.权利要求5的方法，其中所述聚酯含有70至100％mol的从对苯二甲酸乙二醇酯得到的重复单元。
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| US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
| US7776942B2 (en) * | 2005-09-16 | 2010-08-17 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron |
| US7655746B2 (en) * | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US9267007B2 (en) * | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
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| US20070260002A1 (en) * | 2006-05-04 | 2007-11-08 | Zhiyong Xia | Titanium nitride particles, methods of making them, and their use in polyester compositions |
| US7709595B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
| US7709593B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
| US7745368B2 (en) * | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
| US20080027207A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents |
| US20080058495A1 (en) * | 2006-09-05 | 2008-03-06 | Donna Rice Quillen | Polyester polymer and copolymer compositions containing titanium and yellow colorants |
| US8563677B2 (en) * | 2006-12-08 | 2013-10-22 | Grupo Petrotemex, S.A. De C.V. | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
| FR2913210B1 (fr) * | 2007-03-02 | 2009-05-29 | Sidel Participations | Perfectionnements a la chauffe des matieres plastiques par rayonnement infrarouge |
| FR2917005B1 (fr) * | 2007-06-11 | 2009-08-28 | Sidel Participations | Installation de chauffage des corps de preformes pour le soufflage de recipients |
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| TW201435830A (zh) | 2012-12-11 | 2014-09-16 | 3M Innovative Properties Co | 不顯眼之光學標籤及其方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4420581A (en) * | 1979-03-19 | 1983-12-13 | Eastman Kodak Company | Thermoplastic polyester molding compositions |
| US4250078A (en) * | 1979-03-19 | 1981-02-10 | Eastman Kodak Company | Thermoplastic polyester molding compositions |
| US4408004A (en) * | 1982-02-24 | 1983-10-04 | The Goodyear Tire & Rubber Company | High clarity, low haze polyesters having reduced infrared heat-up times |
| US4481314A (en) * | 1983-06-29 | 1984-11-06 | Eastman Kodak Company | Infrared radiation absorbent anthraquinone derivatives in polyester compositions |
| IL72879A (en) * | 1984-09-06 | 1988-12-30 | Ginegar Kibbutz | Plastic sheeting |
| US4731400A (en) * | 1984-12-18 | 1988-03-15 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition |
| JPH02281070A (ja) * | 1989-04-21 | 1990-11-16 | Showa Denko Kk | ポリエチレンテレフタレート樹脂組成物 |
| GB8926631D0 (en) * | 1989-11-24 | 1990-01-17 | Ici Plc | Polymer compositions |
| US5278023A (en) * | 1992-11-16 | 1994-01-11 | Minnesota Mining And Manufacturing Company | Propellant-containing thermal transfer donor elements |
| JP3024495B2 (ja) * | 1994-10-21 | 2000-03-21 | ジェイエスアール株式会社 | レーザーマーキング用樹脂組成物 |
| US5695907A (en) * | 1996-03-14 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Laser addressable thermal transfer imaging element and method |
-
1999
- 1999-01-15 US US09/232,307 patent/US6022920A/en not_active Expired - Lifetime
- 1999-01-19 WO PCT/US1999/001050 patent/WO1999037708A1/en active IP Right Grant
- 1999-01-19 EP EP99903168A patent/EP1049738B1/en not_active Expired - Lifetime
- 1999-01-19 BR BR9907157-6A patent/BR9907157A/pt not_active IP Right Cessation
- 1999-01-19 CN CNB998022489A patent/CN1161402C/zh not_active Expired - Lifetime
- 1999-01-19 CA CA002314966A patent/CA2314966C/en not_active Expired - Lifetime
- 1999-01-19 JP JP2000528619A patent/JP2002501097A/ja active Pending
- 1999-01-19 ES ES99903168T patent/ES2257030T3/es not_active Expired - Lifetime
- 1999-01-19 DE DE69930502T patent/DE69930502T2/de not_active Expired - Lifetime
- 1999-01-19 CN CNB2004100694521A patent/CN1286910C/zh not_active Expired - Lifetime
- 1999-01-22 AR ARP990100263A patent/AR014466A1/es active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| AR014466A1 (es) | 2001-02-28 |
| CN1566209A (zh) | 2005-01-19 |
| EP1049738A1 (en) | 2000-11-08 |
| CN1161402C (zh) | 2004-08-11 |
| CN1288477A (zh) | 2001-03-21 |
| DE69930502D1 (de) | 2006-05-11 |
| ES2257030T3 (es) | 2006-07-16 |
| BR9907157A (pt) | 2000-10-24 |
| CA2314966A1 (en) | 1999-07-29 |
| US6022920A (en) | 2000-02-08 |
| WO1999037708A1 (en) | 1999-07-29 |
| EP1049738B1 (en) | 2006-03-22 |
| JP2002501097A (ja) | 2002-01-15 |
| CA2314966C (en) | 2004-10-19 |
| DE69930502T2 (de) | 2006-08-24 |
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