CN1254348A - 键合的紫外光吸收剂 - Google Patents
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Abstract
公开了低聚物材料,它包含紫外光吸收化合物通过酯键或酰胺键共价键合到低聚物主链上。这些紫外光吸收低聚物可以与聚合物(如聚烯烃)混合,以提供抗紫外光不良影响的保护。
Description
发明的领域
本发明涉及含有与低聚物主链共价键合的紫外光吸收化合物(UVAs)的低聚物。本发明还涉及使用这些低聚物对聚合物或其它基材进行稳定化,以防光化降解。
发明的背景
许多塑料制品在暴露于阳光或其它紫外光源下时容易发生降解。暴露在紫外光源下会引起例如丧失拉伸强度、脆化和变色。为了帮助防止这种降解,通常向聚合物组合物中加入紫外光稳定剂,它用作下面材料的保护顶层。这些紫外光稳定剂的性能良好,但是通常会出现在聚合物中不稳定或者与聚合物不相容的问题,这会使得稳定剂通过浸出、迁移、汽化或其它方式从聚合物中分离出去。如此降低紫外光稳定剂的含量时,它的保护效果会变小,导致聚合物和下面材料的降解。
用作紫外光吸收剂的分子是本领域通常已知的。例如,在Rody等人的美国专利No.4,853,471中说明了将2-(2-羟基苯基)-苯并三唑类化合物用作紫外光吸收剂。这些化合物被描述成能够用来对较宽范围内的聚合物材料进行稳定化以防紫外光,特别是那些用于制备照相材料的聚合物材料。其它种类的紫外光吸收剂包括2-羟基二苯甲酮和二苯基氰基丙烯酸酯类。
虽然这些化合物已知能够吸收紫外光,但是它们与通常用作多层片材顶膜的聚烯烃不相容,这限制了它们在这类结构中的应用。典型的紫外光吸收剂在聚烯烃中溶解度低且流动性高,这使得这些化合物不能以高含量存在于聚烯烃膜中;这些化合物往往容易浮散(bloom)或迁移出聚烯烃膜,从而丧失了化合物的保护性能。
人们作了大量努力来研制将紫外光稳定剂化合物保持在选定的聚合物基质中的方法。已研制出具有可聚合官能度的紫外光稳定剂,然后将可聚合的稳定剂作为共聚单体掺入聚合物中或者与另一种单体共聚,形成能够加入所需聚合物中的稳定聚合物。因为这样稳定化合物就成为聚合物主链的一部分,所以它能保持在聚合物组合物中,并且稳定作用能可长时间保持。将稳定单体掺入聚合物主链中的例子可见于例如Vogl等的聚合物(POLYMER),卷26,页1288(1985);美国专利Nos.3,313,866(Horton等)、4,128,536(Brodsky等)和4,528,311(Beard等)。
人们还研制出通过选择具有能与聚合物中各种官能度反应的基团的紫外光吸收剂,将紫外光吸收化合物连接到聚合物主链上。Fu等人的美国专利No.4,413,096说明了α-烯烃共聚物,其中受阻胺光稳定剂悬挂在聚合物主链上。Fu的共聚物可以通过用受阻胺光稳定化合物对聚合物进行酯基转移反应而制得。
在本领域中仍然需要用紫外光吸收化合物对聚合物(如聚烯烃)进行稳定的方法,向聚烯烃和包含聚烯烃的制品提供持久的保护。
发明概述
我们发现,羟基或胺官能的紫外光吸收化合物能够与羧基官能的低聚物形成共价键合。这一共价键合使得我们能将相容的非挥发性紫外光吸收剂加入聚烯烃型聚合物中。因此,本发明提供了一种紫外光吸收低聚物,它由包含羧基官能的低聚物与羟基或胺官能的紫外光吸收化合物的反应产物的紫外光吸收低聚物组成,其中紫外光吸收化合物是化学式(I)、(II)、(III)或(IV)的化合物: 其中,每个R1各自是卤素、羟基、直链或支链C1-12烷基、直链或支链C2-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Y是C1-18亚烷基或C2-18亚烯基,可以是直链或支链的,中间可以插入一个或多个其中,每个R2各自是H或者直链或支链的C1-6烷基;Z是-OH或-NH2。
本发明还提供了含有所述紫外光吸收低聚物和聚烯烃的聚合物组合物,以及含有由所述聚合物组合物制成膜的制品,如逆向反射片、适顺性路面标志和标记。
本发明在这一方面提供了一种适顺性标志片(conformable marking sheet),它包含一层聚合物膜顶层、一层基层、一层压敏粘合剂层和一层剥离衬垫,所述膜顶层具有部分嵌入其中的玻璃微球和防滑颗粒,该膜包含聚烯烃和本发明的紫外光吸收低聚物;所述基层含有可变形的热塑性聚合物和非增强性无机颗粒(mineralparticulate)。
本发明的另一方面提供了一种封闭式透镜(enclosed-lens)逆向反射片,它包含固定在粘结剂层上的一层透镜、位于透镜层下的一层镜面反射层和包含聚合物膜的一层顶层,所述聚合物膜包含聚烯烃和本发明的紫外光吸收低聚物。
除非另外说明,所有的百分数是以组合物总重量计的重量百分数。
发明的详细说明
本发明的紫外光吸收低聚物通常是将含羧基的低聚物与羟基或胺官能的紫外光吸收化合物反应制得的。羧基官能的低聚物含有至少一个具有羧基(-COOH)侧基的单体。能用于形成本发明紫外光吸收低聚物的羧基官能低聚物通常的重均分子量约为100至10,000,较好约为1000至3500。低聚物的酸值(中和1克低聚物所需的KOH毫克数)通常约为40至180。
用于形成羧基官能低聚物的单体包括烯类不饱和羧酸。羧基官能低聚物可以是这些含羧基单体的均聚物或共聚物。共聚物可以含有不同的含羧基单体,或者可以含有一种含羧基单体和一种不含羧基单体。可用的不含羧基单体类型的例子包括烯类不饱和羧酸酯、烯烃、乙烯基化合物等。
合适的烯类不饱和羧酸包括最多含20个碳原子的烯和芳烯的一、二和三羧酸,以及具有更多数目羧基的酸。这些酸的例子包括丙烯酸、甲基丙烯酸、富马酸、马来酸、巴豆酸、衣康酸和肉桂酸。其中较好的是丙烯酸和甲基丙烯酸。
可用来制备羧基官能聚合物的共聚单体包括烯烃类,如乙烯、丙烯和丁烯;最多含20个碳原子的烯类不饱和芳族单体,如苯乙烯和乙烯基甲苯;总共含最多20个碳原子的羧酸烯类不饱和酯,如乙酸乙烯酯;等等。其中较好的一类共聚单体是烯烃,特别好的是乙烯。
每个R5各自是H或者直链或支链的C1-6烷基;选择a、b和c使其得到约100至10,000的重均分子量,条件是c至少为1。
特别好的羧基官能低聚物是重均分子量约为1000至3500的乙烯-丙烯酸共聚物。较佳的乙烯-丙烯酸共聚物的市售例子包括Allied Signal Inc.,Morristown,NJ的A-C共聚物。
羧基官能低聚物可以用本领域已知的聚合方法制备。例如参见Knutson等的美国专利No.3,658,741,该专利的内容参考结合于本发明中。关于聚合物和低聚物制备的更详细的信息可见于例如聚合物科学和工程大全(Encyclopedia ofPolymer Science and Engineering)卷6,Wiley & Sons 1986,页383-429。
羧基官能低聚物与一种或多种羟基或胺官能紫外光吸收化合物反应,制得本发明的紫外光吸收低聚物。本发明所用的这些紫外光吸收化合物除了吸收紫外光以外,较好的是对于可见光是透明的。可用类型的羟基和胺官能紫外光吸收化合物包括含有羟基和胺的2-羟基苯基苯并三唑、2-羟基二苯甲酮和二苯基氰基丙烯酸酯类(diphenylcyanoacrylates)。
任何含有羟基端基或胺端基的2-羟基苯基苯并三唑紫外光吸收化合物都可以用作本发明的材料。合适的2-羟基苯基苯并三唑化合物包括具有以下化学式(I)的化合物:其中,每个R1各自是卤素、羟基、直链或支链的C1-12烷基或C2-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Y是C1-12亚烷基或C2-12亚烯基,可以是直链或支链的,中间可以插入一个或多个-O-、-C(O)-、-C(O)O-、-OC(O)-、-NR2-、-C(O)NR2-或-NR2C(O)基团;Z是OH或NH2;R2是H或者直链或支链的C1-6烷基;
其它有用类型的紫外光吸收化合物是2-羟基二苯甲酮。只要含有羟基端基或胺端基,任何2-羟基二苯甲酮紫外光吸收化合物都可以使用。可用于本发明的2-羟基二苯甲酮化合物的例子包括化学式(II)和(III)的化合物:其中,每个R1各自是卤素、羟基、直链或支链C1-12烷基、直链或支链C2-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Z是OH或NH2;Y是C1-12亚烷基或亚烯基,可以是直链或支链的,中间可以插入一个或多个-O-、-C(O)-、-C(O)O-、-OC(O)-、-NR2-、-C(O)NR2-或-NR2C(O)基团;R2是H或者直链或支链的C1-6烷基。
也可以使用二苯基氰基丙烯酸酯紫外光吸收化合物,只要这些化合物含有羟基端基或胺端基。有用的二苯基氰基丙烯酸酯化合物的例子包括化学式(IV)的化合物:其中,每个R1各自是卤素、羟基、直链或支链C1-12烷基、直链或支链C1-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Z是OH或NH2;Y是C1-12亚烷基或亚烯基,可以是直链或支链的,中间可以插入一个或多个-O-、-C(O)-、-C(O)O-、-OC(O)-、-NR2-、-C(O)NR2-或-NR2C(O)基团;R2是H或者直链或支链的C1-6烷基。
这些紫外光吸收化合物的任意两种的二聚物也可以使用。
还可以使用其它紫外光吸收化合物,只要它们含有羟基端基或胺端基。这些化合物的例子包括对羟基苯甲酸酯和三嗪。羟基或胺官能紫外光吸收化合物可以单独或组合用于本发明的低聚物、材料和膜中。
本发明的紫外光吸收低聚物可以通过羧基官能低聚物和羟基或胺官能紫外光吸收化合物反应而制得。无需溶剂,反应可以在熔融或液态低聚物中进行,但是如有必要可使用有机溶剂。
反应通常如下进行:在反应器中混合羧基官能低聚物、羟基或酰胺官能紫外光吸收化合物以及适当的催化剂。边搅拌边将混合物加热至低聚物熔融。在升高温度(如220-240℃)下可以连续搅拌,直至不存在未反应的UVA。用TLC(薄层色谱法)或其它适当的方法监控反应混合物,直至确定反应完全。
羧基官能低聚物和羟基或胺官能紫外光吸收化合物是以选定比例存在的,以使得低聚物中填充有所需量的紫外光吸收剂。含量较好是低聚物总重量的约2-25%(重量),尽管可以根据特定的最终用途使用更高或更低的含量。
该反应在有效的酯化催化剂的存在下进行,这些催化剂例如氧化二丁基锡、氢氧化二丁基锡、氢氧化氧化丁基锡(butyl tin oxide hydroxide)、辛酸亚锡、蓖麻油酸锂和新癸酸铋。较好的催化剂是氢氧化氧化丁基锡(FASTCAT 4100,购自Atochem North America,Inc.,Philadelphia,PA)。催化剂通常占反应混合物的约0.01-5.0%(重量),较好约占0.1-1.0%(重量),尽管根据所用的特定催化剂会需要稍多或稍少的用量。
如此形成的紫外光吸收低聚物可以就这么使用或者混入聚合物(如聚烯烃)中,它还可以按照需要进一步进行加工。例如,它们可以形成耐久的膜,为下面的基质或材料提供保护,以防紫外光的不良影响。
本发明的聚合物材料是通过混合本发明的紫外光吸收低聚物和聚合物(如聚烯烃)而制得的。因为紫外光吸收剂是共价键合在低聚物上的,所以它不会浮散和迁移出聚烯烃膜,从而提高了结构中使用该材料制得膜制品的使用寿命。
可用于本发明聚合物材料的聚烯烃包括由至少一种烯属单体制得的聚合物。这些烯属单体的例子包括乙烯、丙烯、丁烯、苯乙烯等,较好的烯属单体是乙烯。
聚烯烃可以是烯属单体的均聚物,或者可以是不同烯属单体的共聚物,或者一种烯属单体与另一种单体的共聚物。共聚单体可以是任何一种能够与烯属单体共聚的单体,只要该单体不会导致不相容于紫外光吸收低聚物。有用的共聚单体类型包括烯类不饱和羧酸;烯类不饱和羧酸酯和含乙烯基的单体。较好的一类共聚单体是烯类不饱和羧酸,特别好的是丙烯酸。
聚合物材料是通过将本发明的紫外光吸收低聚物与聚烯烃混合制得的。紫外光吸收低聚物的通常存在量应足够高以致于能提供防紫外光的保护,但又不会高得使其迁移、分离或浮散出聚烯烃。聚合物材料通常含有足够量的紫外光吸收低聚物,以提供占材料总重量约0.05-50%(重量),较好约1-20%(重量)的紫外光吸收化合物。
聚合物材料可如下制得:边搅拌边混合聚烯烃熔体和紫外光吸收低聚物熔体,直至混合物均匀。达到均匀度以后,可以用本领域已知的方法将混合物挤压成或形成膜或其它形状。膜还可以通过将聚烯烃聚合物和紫外光吸收低聚物共挤出直接形成膜而制得。
含有本发明聚合物材料的膜可以用作多层逆向反射片的顶层或覆盖膜。逆向反射片是本领域中熟知的,可参见例如Bailey等的美国专利No.4,767,659,于此参考结合于本发明中。所述聚合物膜为逆向反射片的下层提供抗紫外光的保护,因此延长了逆向反射片和包括有该逆向反射片的制品的使用寿命。
当用作逆向反射片顶层时,该聚合物膜除了提供对紫外光的保护能力以外,还应该具有足够的可伸展性以承受较大的拉伸(如牌照的压花),具有足够的柔性以防在拉伸以适顺不规则表面时发生局部脱层,还应该具有良好的抗冲击性。当用作逆向反射片的顶层时,该聚合物膜较好的是具有至少约100%的伸长率,良好的耐冲击性、韧性和透明度。
含有本发明聚合物膜作为顶层的逆向反射片通常包含多层。合适的逆向反射片的一个例子是片材制品,它含有一层粘结剂层;一层全部或部分嵌入粘结剂层中的玻璃微球;一层镜面反射层和一层由可除去的衬垫覆盖的粘合剂层。如有必要也可以存在其它层。
为了使用本发明的聚合物膜制备逆向反射片,将该膜层压到含上述多层的逆向反射基材上。
用本发明聚合物膜制得的逆向反射片可用于较宽范围的制品,包括交通标志、栏障、锥形路标和压花的牌照或信息牌。压花的信息牌的制备描述于美国专利Nos.5,085,918和5,227,194中,其内容参考结合于本发明中。
本发明的膜还可用于制备适顺性路面标志片。这些适顺性标志片描述于Lasch等的美国专利No.5,194,113中,其内容参考结合于本发明中。
当用于制备适顺性标志片时,聚合物膜应该具有足够的延性以使得标志片能够适顺于路面或其它底材的表面以提高标志片对底材的粘合力。当用作适顺性标志片的顶层时,聚合物膜较好的是包括增强可见度的颜料,如二氧化钛或铬酸铅。
聚合物膜顶层片或顶层可以直接挤出或层压到适顺性片材的其它层上,或者在顶层和片材的其它层之间插入一层粘合剂层或其它层。
本发明的聚合物膜还可以用作不依赖于适顺层的标志片。如果这样使用的话,聚合物膜可以层压到压敏粘合剂层上以提高对路面或其它底材的粘合力。还可以存在有剥离衬垫,以便于处理和贮存。另外,可以有颗粒全部或部分地嵌入膜的顶表面中,以提高膜的逆向反射性和/或防滑性能。
本发明还参考以下实施例加以说明,这些实施例应被理解为仅用于说明而不是限制本发明。
实施例
实施例1
本实施例使用Allied-Signal A-C 5120低聚物,它是约15%丙烯酸和85%乙烯的共聚物,其重均分子量约为1500,羧酸当量约为475,以及购自BASF Inc.,Ludwigshafen,Germany的UvinulX-19,即2-羟基-4-(2-羟基乙氧基)二苯甲酮。
紫外光吸收低聚物如下制备:将25克A-C 5120放入100毫升的三颈圆底烧瓶中。加入10克UvinulX-19和0.008克Fastcat4100氢氧化丁基锡催化剂,不使用溶剂。对反应混合物进行搅拌并加热至150℃,形成均匀的熔体。在液面以下喷射氮气,继续加热直至温度达到220℃,将混合物保持在220-230℃,搅拌4个小时。在4个小时之后,TLC(50%乙酸乙酯/50%己烷)显示几乎没有未反应的二苯甲酮。熔融混合物从烧瓶倒入铝盘中,使其冷却至室温。
实施例2
将25克粉状的实施例1产物与490克购自Dow Chemical,Midland MI的Primacor3440(聚乙烯-丙烯酸共聚物)进行干混。将共混物挤出在聚酯载体上成为标称厚度为2密耳(51微米)的膜,温度分布为区1-350°F(177℃),区2-380°F(193℃),区3和模头-420°F(216℃)。熔体温度为306°F(152℃)。在Haake3/4″单螺杆挤出机上挤出。膜的UVA填充量为1.2%(重量)。
以上说明书、实施例和数据对本发明组合物的制备和使用作了完整的说明。由于在不偏离本发明的精神和范围的情况下,本发明可以有许多的实施方案,因此本发明属于以下所附的权利要求书。
Claims (24)
2.如权利要求1所述的紫外光吸收低聚物,其中化学式(I)、(II)、(III)或(IV)的化合物占所述低聚物的约1-25%(重量)。
3.如权利要求1所述的紫外光吸收低聚物,其中至少一种紫外光吸收化合物是化学式(I)的化合物。
5.如权利要求1所述的紫外光吸收低聚物,其中至少一种紫外光吸收化合物是化学式(II)的化合物。
6.如权利要求1所述的紫外光吸收低聚物,其中至少一种紫外光吸收化合物是化学式(III)的化合物。
8.如权利要求1所述的紫外光吸收低聚物,其中至少一种紫外光吸收化合物是化学式(IV)的化合物。
9.一种聚合物材料,它包含聚烯烃和紫外光吸收低聚物,所述紫外光吸收低聚物包含羧基官能低聚物与羟基或胺官能紫外光吸收化合物的反应产物,其中所述紫外光吸收化合物是化学式(I)、(II)、(III)或(IV)的化合物:其中,每个R1各自是卤素、羟基、直链或支链C1-12烷基、直链或支链C2-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Y是C1-18亚烷基或C2-18亚烯基,可以是直链或支链的,中间可以插入一个或多个其中,每个R2各自是H或者直链或支链的C1-6烷基;Z是-OH或-NH2。
10.如权利要求9所述的聚合物材料,其中聚烯烃包括乙烯-丙烯酸共聚物。
11.如权利要求9所述的聚合物材料,其中至少一种紫外光吸收化合物是化学式(I)的化合物。
12.如权利要求9所述的聚合物材料,其中至少一种紫外光吸收化合物是化学式(II)的化合物。
13.如权利要求9所述的聚合物材料,其中至少一种紫外光吸收化合物是化学式(III)的化合物。
14.如权利要求9所述的聚合物材料,其中至少一种紫外光吸收化合物是化学式(IV)的化合物。
15.一种聚合物膜,它包含权利要求9所述的聚合物材料。
16.一种保护底材以防紫外光影响的方法,该方法包括将聚合物膜施用到底材上,所述聚合物膜包含聚烯烃以及羧基官能低聚物与羟基或胺官能紫外光吸收化合物的反应产物,其中所述紫外光吸收化合物是化学式(I)、(II)、(III)或(IV)的化合物:其中,每个R1各自是卤素、羟基、直链或支链C1-12烷基、直链或支链C2-12烯基、直链或支链C1-12烷氧基、直链或支链C2-12烯氧基、直链或支链C1-12烷醇、氨基、直链或支链C1-12烷基氨基或者直链或支链C1-12二烷基氨基;Y是C1-18亚烷基或C2-18亚烯基,可以是直链或支链的,中间可以插入一个或多个其中,每个R2各自是H或者直链或支链的C1-6烷基;Z是-OH或-NH2。
17.如权利要求16所述的方法,其中聚烯烃包括乙烯-丙烯酸共聚物。
18.如权利要求16所述的方法,其中羧基官能聚合物包括乙烯-丙烯酸共聚物。
19.如权利要求16所述的方法,其中羧基官能聚合物包括丙烯酸、甲基丙烯酸,或者它们的共聚物。
20.如权利要求16所述的方法,其中紫外光吸收化合物含有苯并三唑基团。
21.如权利要求16所述的方法,其中紫外光吸收化合物含有二苯甲酮基团。
22.一种适顺性标志片,它包含:
(a)一层聚合物膜顶层,该层具有部分嵌入其中的玻璃微球和防滑颗粒,该膜包含聚烯烃和权利要求1的紫外光吸收低聚物;
(b)一层基层,它包含可变形的热塑性聚合物和非增强性无机颗粒;
(c)一层压敏粘合剂层;和
(d)一层剥离衬垫。
23.一种封闭式透镜逆向反射片,它包含固定在粘结剂层上的一层透镜、位于透镜层下的一层镜面反射层和包含聚合物膜的一层顶层,所述聚合物膜包含聚烯烃和权利要求1的紫外光吸收低聚物。
24.一种反射标志,它包含权利要求23的逆向反射片。
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-
1997
- 1997-04-29 US US08/841,062 patent/US6008302A/en not_active Expired - Lifetime
- 1997-08-25 CN CN97182143A patent/CN1117771C/zh not_active Expired - Fee Related
- 1997-08-25 AU AU40870/97A patent/AU726462B2/en not_active Ceased
- 1997-08-25 JP JP54692998A patent/JP2002504163A/ja not_active Ceased
- 1997-08-25 DE DE69717313T patent/DE69717313T2/de not_active Expired - Fee Related
- 1997-08-25 CA CA002287997A patent/CA2287997A1/en not_active Abandoned
- 1997-08-25 WO PCT/US1997/014926 patent/WO1998049207A1/en active IP Right Grant
- 1997-08-25 EP EP97938574A patent/EP0980395B1/en not_active Expired - Lifetime
-
1999
- 1999-08-11 US US09/371,985 patent/US6235375B1/en not_active Expired - Lifetime
-
2001
- 2001-04-02 US US09/824,303 patent/US6464817B2/en not_active Expired - Lifetime
-
2002
- 2002-07-22 US US10/200,797 patent/US6582790B2/en not_active Expired - Fee Related
Cited By (3)
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CN103842591A (zh) * | 2011-09-01 | 2014-06-04 | 3M创新有限公司 | 道路标记材料和方法 |
CN103842591B (zh) * | 2011-09-01 | 2016-03-16 | 3M创新有限公司 | 道路标记材料和方法 |
CN103535215A (zh) * | 2012-07-13 | 2014-01-29 | 三菱树脂株式会社 | 农业用多层膜 |
Also Published As
Publication number | Publication date |
---|---|
CN1117771C (zh) | 2003-08-13 |
JP2002504163A (ja) | 2002-02-05 |
WO1998049207A1 (en) | 1998-11-05 |
DE69717313D1 (de) | 2003-01-02 |
DE69717313T2 (de) | 2003-08-21 |
EP0980395B1 (en) | 2002-11-20 |
US6464817B2 (en) | 2002-10-15 |
US6235375B1 (en) | 2001-05-22 |
EP0980395A1 (en) | 2000-02-23 |
CA2287997A1 (en) | 1998-11-05 |
US20010016241A1 (en) | 2001-08-23 |
AU4087097A (en) | 1998-11-24 |
US20030012912A1 (en) | 2003-01-16 |
US6582790B2 (en) | 2003-06-24 |
US6008302A (en) | 1999-12-28 |
AU726462B2 (en) | 2000-11-09 |
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