CN1196502C - 除臭吸收性片材 - Google Patents
除臭吸收性片材 Download PDFInfo
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- CN1196502C CN1196502C CN99808986.9A CN99808986A CN1196502C CN 1196502 C CN1196502 C CN 1196502C CN 99808986 A CN99808986 A CN 99808986A CN 1196502 C CN1196502 C CN 1196502C
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- deodorizer
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- absorbent sheet
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Abstract
一种具有嵌于纤维网(4)中的水不溶性除臭剂(2)和吸收性聚合物(3)的除臭吸收性片材(1),其中吸收性聚合物(3)被固定于构成纤维网(4)的纤维之上,同时除臭剂通过吸收性聚合物(3)被固定于所述纤维网(4)内,在片材(1)的表面上基本没有除臭剂和吸收性聚合物。
Description
技术领域
本发明涉及一种除臭吸收性片材,它适于作为吸收性物品,宠物厕所衬垫等中的吸收体。
背景技术
已知这种类型的除臭吸收性片材包括如日本专利申请公开第142256/82号中所述的卫生巾用吸收体,其包含一种由两片含有活性炭的吸收性纸包夹的吸收性聚合物;以及如日本专利申请公开第281042/96号中所述的除臭片材,其是如下制得的:在涂有热熔性粘合剂的纸片之间分散活性炭,然后将它们结合为一体。
在具有上述结构的吸收体中,用于吸收并保持液体的含有吸收性聚合物的层与用于除臭的含有活性炭的层相互分隔。因此,对于被吸收并保持的液体来说,除臭作用仅能间接地进行,使得除臭效果不能令人满意。为获得足够的除臭效果,可能需要大量的除臭剂如活性炭,在这种情况下除臭剂可能在卫生巾使用期间脱落。
而且上述文献所公开的吸收体中含有吸收性聚合物的层所具有的结构是吸收性聚合物颗粒仅包夹于两层吸收性纸之间。因此,为增进吸收效果而增加的吸收性聚合物有可能在卫生巾使用期间脱落。
发明公开
因此,本发明的一个目的是提供一种具有高度吸收性能和高度除臭性能的除臭吸收性片材。
本发明的另一个目的是提供一种除臭吸收性片材,它可以包含增加用量的除臭剂和吸收性聚合物,而不必担心脱落现象的出现。
本专利的发明者们已经发现,将除臭剂和吸收性聚合物以混合物形式嵌入纤维网内部并利用吸收性聚合物的粘着性固定除臭剂,可以达到上述目的。
本发明提供一种具有嵌于纤维网中的水不溶性除臭剂和吸收性聚合物的除臭吸收性片材,其中吸收性聚合物被固定于构成纤维网的纤维之上,同时除臭剂通过吸收性聚合物被固定于纤维网内,在片材的表面上基本没有除臭剂和吸收性聚合物。
本发明还提供一种制造上述除臭吸收性片材的优选方法,其包括以下步骤:在湿的下层纤维片上同时或以任何顺序连续地分散吸收性聚合物和除臭剂,在其上覆盖上层纤维片,然后通过干燥将上层和下层纤维片合结为一体的步骤。
附图简述
图1是显示本发明中一个实施方案的除臭吸收性片材的结构的示意图。
图2是显示一种优选用于制造本发明除臭吸收性片材的装置的示意图。
图3是显示用于评价吸收性的卫生巾的结构的剖视图。
图4是一个女性臀部运动模型的示意图,它用于评价吸收性。
本发明的最佳实施方式
以附图为参考以下将描述本发明除臭吸收性片材的优选实施方案。
图1是显示本发明中一个实施方案的除臭吸收性片材的结构的示意图。
图1所示的除臭吸收性片材1所具有的结构是:水不溶性除臭剂2和吸收性聚合物3构成嵌于纤维网4内的一层。即,除臭吸收性片材1具有单层结构,这种结构与以上背景技术中所描述的用于日本专利申请公开第142256/85号中所述的卫生巾结构,即吸收性聚合物颗粒由两层吸收性纸包夹的双层吸收性纸结构完全不同。
在除臭吸收性片材1中,除臭剂2通过聚合物3粘附并固定于构成纤维网4的纤维上。在纤维网4的表面上基本没有除臭剂2和聚合物3。此处采用术语“基本没有(或者基本不存在)”用于表示除臭剂2和聚合物3不是明显存在的,但对于除臭吸收性片材1的制造中不可避免混入的痕量除臭剂2和聚合物3则是可以接受的。
不受任何具体理论的限制,除臭剂2通过聚合物3的粘附和固定被认为是以下现象(1)至(4)的互相补充的结果。
(1)聚合物3吸水并膨胀导致变形。更具体而言,聚合物3吸水后膨胀并***,使得改变其形状而适应于聚合物3附近的纤维或除臭剂2之形状,然后聚合物3粘附并固定于纤维或除臭剂2之上。有时多个聚合物3相互粘附,将纤维或除臭剂2闭锁。但由于聚合物3具有高的凝胶强度,所以除臭剂2的整个表面不会完全被聚合物3覆盖,从而防止了除臭剂3之除臭性能的下降。在对闭锁纤维或除臭剂2的聚合物3进行干燥时,聚合物闭锁纤维或除臭剂2的状态在干燥后并未改变,所以聚合物3牢固地粘附于纤维或除臭剂2之上。甚至对于仅微弱粘附并固定纤维或除臭剂2的聚合物3进行干燥时,因粘附和固定(即锚定效应)以及分子间作用力所造成的聚合物3的嵌入使得聚合物3与纤维或除臭剂2的结合具有足够强度。
(2)聚合物3膨胀并变粘,有助于上述现象(1)的体现。
(3)聚合物3中的极性基团,特别是羧基构成氢键。因此当纤维和除臭剂2具有极性基团时,膨胀并粘附纤维或除臭剂2的聚合物3在聚合物3和纤维或除臭剂2之间构成了氢键,结果导致聚合物3与纤维或除臭剂2牢固键合。
(4)聚合物3以细颗粒形式分散于片材1内部的全部区域。因此以上现象(1)、(2)和(3)发生于片材1的每一部位,从而有效地防止了除臭剂2的脱落。
除臭剂2和聚合物3分散于组成纤维网4的纤维所构成的空间内,并在纤维网4的厚度方向上以预定厚度分布。换而言之,除臭剂2和聚合物3被分散于纤维网4中构成三维结构层,使得可以充分发挥其吸收和除臭功能,同时有效地防止了聚合物3出现胶凝堵塞的现象。
如图1所示,除臭剂2和聚合物3以相互混合的状态存在于纤维网4的内部。因此,除臭吸收性片材1在同一位置实行吸收并保持液体的功能以及对液体除臭的功能,显现出了显著增加的除臭效能。即,在除臭吸收性片材1中同时进行了吸收并保持液体及对液体的除臭。此外,如上所述,由于除臭剂2被固定于整体式构成的片中,在采用大量除臭剂以增加除臭效能的情况下不必担心除臭剂2脱落。如以下所述,这对于使用黑色粉末如活性炭的情况是十分有益的。
由于聚合物3也粘附并固定于构成纤维网4的纤维上,对于使用大量聚合物以增加吸收效能的情况不必担心聚合物脱落。这对于通过加入增加量的聚合物3并降低纤维网4的厚度以获得薄的除臭超强吸收性片材的情况是十分有益的。在这种情况下,虽然最理想的情况是所有聚合物3被固定于纤维之上,但如果至少50wt%、特别是70wt%或更多的聚合物3被固定于纤维之上,就可以有效防止脱落。
虽然除臭剂2和聚合物3的重量比需要依据除臭吸收性片材1的用途等因素而定,但由于以下原因,一般来说优选的情况是除臭剂与聚合物重量比(前者/后者)范围在1/10至10/1之间,特别优选为1/3至3/1。当重量比为1/10或更高时,对于聚合物3所吸收的液体以及存在于其周围的液体具有足够的除臭效果。当重量比为10/1或更低时,除臭剂2颗粒可充分固定于聚合物3之上,从而有效防止了从除臭吸收性片材1上脱落。
依据上述重量比范围决定所分散除臭剂2和聚合物3用量的作法是优选的。具体而言,除臭剂2优选以3至500g/m2、特别是20至100g/m2的用量进行分散,而聚合物3优选以5至500g/m2、特别是20至100g/m2的用量进行分散。以3g/m2或更多的用量进行分散的除臭剂2对于液体吸收表现出有效的除臭性能。当除臭剂的用量不超过500g/m2时,可以确保除臭吸收性片材具有足够的柔软性并且可使成本降至最低。另一方面,当聚合物3以5g/m2或更多的用量进行分散时,除臭剂2充分固定于纤维网4之上。当聚合物3用量不超过500g/m2时,对于片材可有效地进行干燥,同时可有效防止因胶凝堵塞导致的吸收受阻现象。
对于除臭剂2的种类并无特别的限制,只要不溶于水并且具有除臭功能即可。适用的除臭剂的实例有颗粒状或纤维状活性炭,天然矿物(如膨润土、膨润土衍生物、高岭土和水硅钠石),以及合成无机物(如沸石和无定形硅石)。颗粒状活性炭因为相对较便宜并且对于多种散发难闻气味的物质具有稳定的吸收而被优选。在使用颗粒状除臭剂时,为防止从纤维网4中脱落并防止纤维网4被撕裂,其优选粒径为1至800μm,特别为50至600μm。
聚合物3优选为可吸收并保持自重20倍或更多液体而且可以胶凝的材料。这些聚合物包括淀粉、交联的羧甲基化纤维素、丙烯酸或丙烯酸碱金属盐的均聚物或共聚物、聚丙烯酸或其盐、聚丙烯酸盐接枝聚合物。特别优选使用粒径为2至800μm、特别为50至600μm的颗粒状聚合物。
构成纤维网4的纤维包括纤维素类纤维,如天然纤维素,如木纸浆和棉花,以及再生纤维素,如人造丝和铜胺人造丝。热塑性纤维的细纤维或短纤维也可以使用。从成本角度考虑,纸木浆是优选的。针叶木牛皮纸桨(NBKP)更为优选。特别优选的情况是,纤维网4主要由膨松纤维、特别是膨松纤维素类纤维构成,以便于液体的渗透和扩散。此处采用术语“膨松纤维”指具有三维结构的纤维,如扭曲状结构、波浪结构、折叠结构、分枝结构、以及这些结构的复合结构,或是其粗糙度例如小于0.3mg/m的非常粗的纤维。此处采用术语“纤维网”用于指通过纤维间机械缠结、粘合或融合等所形成的片。这些片包括纸、无纺布、以及它们的复合材料。
膨松纤维包括粗糙度为0.3mg/m或更多、特别是0.3-2mg/m的纤维素类纤维。粗糙度为0.3mg/m或更多、纤维圆度为0.5至1的纤维素类纤维也是优选的。通过纤维素类纤维分子间以及分子内交联所得的交联纤维素类纤维也优选作为膨松纤维。对于纤维“粗糙度”是对于粗细不均匀纤维粗度的度量。它可通过例如KAJANNI ELECTRONICS,Ltd制造的纤维粗糙度测量仪FS-200进行测量。
虽然上述纤维素类纤维被用于构成纤维网4,但优选联合使用热熔性粘合纤维以获得湿强度增大的纤维网。以纤维网4计,热熔性粘合纤维的比例为1至50wt%,特别为3至30wt%,热熔性粘合纤维可以是一种在热的作用下能够熔融并相互粘合的材料。此类纤维包括聚烯烃纤维,如聚乙烯、聚丙烯和聚乙烯醇;聚酯纤维;以及复合纤维,如聚乙烯/聚丙烯纤维。特别优选为聚乙烯醇、聚酯等纤维。热熔性粘合纤维一般长度为2至60mm,纤度为0.5至3旦。
纤维网4的基础重量优选为10至200g/m2,特别为15至100g/m2。从湿强度、吸收性能以及除臭性能的性价比方面考虑,除臭吸收性片材1的总基础重量优选为50至500g/m2,特别是60至300g/m2。
以下以附图2为参考描述制造除臭吸收性片材1的优选方法。
图2所示的装置10包含一个用于构成下层纤维片的部件20,一个用于分散粉末的部件30,一个叠加部件40,一个干燥部件50,以及一个卷收部件60。
下层片构成部件20具有一个造纸部件21和一个脱水部件22。通过纸原料进料部件23,纸浆被送入造纸部件21中,在此处下层纤维片5在一个圆筒24上形成。含有大量水的下层纤维片在脱水部件22的吸气盒中被脱水,使得湿的下层纤维片5含水量达预定值。由于以下原因,湿的下层纤维片5的含水量优选在20至500wt%,特别是50至300wt%之间。当下层纤维片5水含量为20%或更多时,分散于其上的吸收性聚合物变得足够粘,可以对其自身以及除臭剂进行固定。当水含量不超过500wt%时,下层纤维片5可在干燥部件50中被充分干燥。优选地,下层纤维片5的基础干重为10至200g/m2,特别为15至100g/m2。
在粉末分散部件30中,除臭剂2和聚合物3被同时或顺序分散于湿的下层纤维片5上,使得聚合物3吸水变粘并粘附和固定于构成下层纤维片5的纤维之上。然后除臭剂粘附于粘性的聚合物3之上并通过聚合物3固定于纤维上。
由于在潮湿情况下构成下层纤维片5的纤维仍具有自由度,纤维间相互不结合,所分散的除臭剂2和聚合物3嵌入纤维所构成的间隙中并按三维方式进行分散。因此,与聚合物和除臭剂保持在两层纸之间的常规片相比,这种结构可以稳定固定住更大量的除臭剂和聚合物。除臭剂2和聚合物3可均匀分散于湿的下层纤维片5的整个表面之上,或根据需要,它们可沿长度方向按间隔的条状或点状方式分散。
对于粉末分散部件30中除臭剂2和聚合物3的分散顺序,除臭剂可先于聚合物或相反顺序、或者它们被同时分散。
在叠加部件40中,预制的干燥上层纤维片6从进料辊41处被展开并叠加于除臭剂2和聚合物3已分散于其上的下层纤维片5之上。因此,除臭剂2和聚合物3被包夹于上层纤维片6和下层纤维片5之间。在这一阶段中,由于下层纤维片5仍为湿态,其组成纤维具有自由度,所以除臭剂2和聚合物3进入下层纤维片5更深,而且下层纤维片5的纤维和上层纤维片6的纤维易于相互缠结。依据所得除臭吸收性片材最终用途等因素,上层纤维片6和下层纤维片5的组成可以相同或不同。上层纤维片6可为多种类型的无纺布,如气流法无纺布、纺粘无纺布、以及射流喷网法无纺布。
接着将叠加有上层纤维片6的下层纤维片5送入Yankee干燥器51中,它在此处被干燥,使得上层和下层纤维片5和6中的纤维进一步缠结,从而使得上层和下层纤维片5和6结合构成纤维网4。氢键和热融合的补充作用使这种结合作用产生一个整体。同时,随干燥的进行除臭剂2和聚合物3的固定进一步进行。因此得到了一种单片结构的除臭吸收性片材,其中除臭剂2和聚合物3嵌入纤维网内。虽然干燥温度需根据纤维种类等因素而定,但一般为100至180℃,特别为105至150℃。所得除臭吸收性片材1在卷收部件60处被卷收成捆。
在采用湿处理纸生产除臭片的常规方法中,活性炭被预先混合并同纸原料进料部件23中的纸浆一起分散并以混合状态进料。与之相反,对于上述本发明的方法来说,其独特的特征在于除臭剂分散在湿的纤维网上,这样可以产生以下效果。(1)片材强度不受损害。(2)除臭剂不会出现于片材的表面上。(3)除臭剂和聚合物被锚定并嵌入纤维网中。
由此制得的本发明除臭吸收性片材不仅适于作为吸收性物品如卫生巾和一次性尿布中的吸收体,也适于作为宠物厕所的衬垫,用于保持和/或解冻冷冻食品的吸收性片材,坐便器的吸收性片材,床垫的吸臭内芯,以及除臭墙纸。
虽然以优选实施方案为参考已对本发明的除臭吸收性片材进行了描述,但应认识到本发明并不仅局限于此,在不背离本发明范围的前提下可以进行多种改变和改进。例如,可以将多种物质如用于改善吸收性的亲水性细纤维或亲水性颗粒加到嵌有除臭剂2和聚合物3的部位中,以此赋予除臭吸收性片材1其它功能。此外,为增加湿强度可以将纸张强化剂如海绵或羧甲基纤维素加到下层和/或上层纤维片中。此外,可将湿的上层片叠加于下层片上以代替叠加干的上层片的作法。
实施例1
将95份粗糙度为0.32mg/m、纤维圆度为0.30的膨松交联纸浆与5份纤度为1旦、长度为3mm的聚乙烯醇纤维(FIBRIBOND(商品名),由SANSHO K.K.制造)分散于水中并混合,以制备具有预定浓度的纸原料。将该原料送入湿法制纸机的造纸部件中,以构成基础干重为20g/m2的下层纤维片。下层纤维片在一吸气盒中脱水,将水含量降低至60wt%。将粒径为300μm的吸收性聚合物基本上均匀地分散于经脱水但仍为湿的纤维片中,其用量为30g/m2,然后以3g/m2的用量基本上均匀分散粒径为300μm的活性炭。将与下层纤维片成分相同的预制上层纤维片(基础重量40g/m2)盖于其上已分散有聚合物和活性炭的下层纤维片上。已盖有吸收性纸的下层纤维片通过Yankee干燥器,在此处于130℃下干燥并结合成一体。由此获得了一种单层的除臭吸收性片材,其中聚合物和活性炭以混合形式嵌于其中。所得片材的基础重量为93g/m2。
实施例2
按与实施例1相同方法获得除臭吸收性片材,只是将活性炭的用量变为90g/m2。
实施例3
按与实施例1相同方法获得除臭吸收性片材,只是再加入3g/m2的粒径为100μm或更小的膨润土。
实施例4
按与实施例1相同方法获得除臭吸收性片材,只是用粗糙度为0.24mg/m、纤维圆变为0.34的膨松针叶木牛皮纸浆(NBKP)(HARMac-R,由MacMilan Bloedel Ltd.制造)代替用于上层和下层纤维片的膨松交联纸浆,并将活性炭用量改为30g/m2。
对照实施例1
将与实施例1用量相等的相同聚合物和活性炭分散于干的下层纤维片上,其中下层片的成份以及基础重量与实施例1的上层纤维片相同。将成分以及基础重量与实施例1中上层纤维片相同的上层纤维片置于其上。将两片加热至130℃获得对照除臭吸收性片材。所得片材不是上层和下层纤维片结合在一起的单层片,而是双层片。
性能评价
为评价实施例以及对照实施例中所得的除臭吸收性片材的性能,按照以下测试方法测量除臭效果以及除臭剂和吸收性聚合物的脱落情况,以及该片材用作卫生巾时的吸收性。
1)除臭效果
使用微量注射器向一个具有玻璃塞的500ml Erlenmeyer烧瓶中注入5μl二乙胺,用塞子塞住烧瓶(该样品称为对照1)。从除臭吸收性片材上裁取5cm×5cm样片并将其置于无纺布制的袋中,该样片作为测试样片。将测试样片放入另一个含有二乙胺的Erlenmeyer烧瓶中并用塞子塞住烧瓶。30分钟后按以下方法测量气味的强度。
出示一个密闭的含有各测试样片的Erlenmeyer烧瓶,一个对照Erlenmeyer烧瓶以及一个空的Erlenmeyer烧瓶(对照2),随机选取25位受试人员并请求他们对气味进行评价。对评价结果进行平均。以下为评价指数以及评价值的平均值的含义。
评价方式
(1)首先闻打开玻璃塞子的对照(2)(无味玻璃瓶);
(2)在闻完(1)后立即按相似方式闻含有测试样片的烧瓶;然后
(3)按相似方式闻对照1。
在(1)、(2)和(3)完成后,受试人员在下列指数中选择其认为最接近于其感受的指数。以(1),(2)和(3)的秩序依次测量各样品。
评价指数
1与对照2(无味)完全相同。
2差不多无味
3气味轻微
4气味与对照1相似
平均值的含义
数值越小,除臭效果越佳,表明烧瓶内容物的气味已经被吸收。
2)吸收性
采用实施例和对照实施例中制得的除臭吸收性片材制备图3所示卫生巾。图3是卫生巾100的截面图。卫生巾100包含一个按图示方式折叠除臭吸收性片材构成的吸收体101,一个由多孔聚乙烯膜(开孔率:20%)构成并包围吸收体101上侧和下侧的表层材102,以及一个由层压有聚乙烯的防水纸构成的底层材103。将卫生巾100安装于女性臀部可移动模型104之上,并穿上内裤。模型按100步/分钟的速度进行行走运动10分钟(相当于行走速度50m/min)。模型104保持行走状态,将5g脱纤维蛋白的马血通过管105注入卫生巾中,并按相同速度继续进行行走运动20分钟(5g-吸收点)。然后再注入5g脱纤维蛋白的马血,然后按相同速度运动20分钟(10g-吸收点)。在十个用于测试的卫生巾中,在各时间点上出现泄漏的卫生巾的数目被作为吸收性指数。
3)除臭剂和聚合物的脱落
将裁成70mm×20mm大小的样品片称重并放入一个具有拉链的280mm长、200mm宽的塑料袋中。在手中将袋子振摇50次对样品进行振动。实验后对样品重新称重。实验前和实验后的重量差别作为除臭剂和聚合物的脱落量。实验后还用裸眼观察样品。测量和观察结果按以下进行分级。
A基本未观察到除臭剂和聚合物脱落(等于或小于0.05g)。
B观察到除臭剂和聚合物轻微脱落(大于0.05g但小于0.15g)。
C观察到除臭剂和聚合物明显脱落(等于或大于0.15g)。
表1
除臭剂 | 除臭效果(臭味强度) | 除臭剂和聚合物的脱落 | 吸收性(泄漏的数目) | ||||||
种类 | 粒径(μm) | 分散量(g/m2) | 除臭剂聚合物 | 脱落量(g) | 裸眼观察 | 5g | 10g | ||
实施例1 | 活性炭 | 300 | 3 | 1/10 | 2.2 | ≤0.01 | A | 0 | 0 |
实施例2 | 活性炭 | 300 | 90 | 3/1 | 1.1 | 0.03 | A | 0 | 0 |
实施例3 | 活性炭膨润土 | 300≤100 | 33 | 2/10 | 2.0 | ≤0.01 | A | 0 | 0 |
实施例4 | 活性炭 | 300 | 30 | 1/1 | 1.6 | 0.03 | A | 0 | 0 |
对照实施例1 | 活性炭 | 300 | 3 | 1/10 | 2.2 | 0.21 | C | 0 | 2 |
从表1所示结果可以看出,实施例(本发明)的除臭吸收性片材在除臭和吸收性方面要明显优于对照片材。尽管本发明的片材含有大量除臭剂和聚合物,这些颗粒难于从片上脱落。
工业可应用性
如以上详述,本发明提供了一种具有高度除臭功能和高度吸收功能的除臭吸收性片材。
本发明还提供了一种除臭吸收性片材,它可以包含大量除臭剂和吸收性聚合物而不必担心颗粒脱落现象的出现。
Claims (4)
1、一种具有嵌于纤维网中的水不溶性除臭剂和吸收性聚合物的除臭吸收性片材,其中所述吸收性聚合物被固定于构成所述纤维网的纤维之上,同时所述除臭剂通过所述吸收性聚合物被固定于所述纤维网内,在所述片材的表面上基本没有所述除臭剂和所述吸收性聚合物,所述除臭剂是颗粒状的且其粒径为50-600μm,并且所述吸收性聚合物是粒径为50-600μm的颗粒状聚合物。
2、如权利要求1所述的除臭吸收性片材,其中除臭剂和吸收性聚合物的重量比(前者/后者)为1/10至10/1。
3、如权利要求1所述的除臭吸收性片材,其中纤维网主要由膨松纤维素类纤维构成。
4、一种制造如权利要求1所述的除臭吸收性片材的方法,其包括以下步骤:在湿的下层纤维片上同时或以任何顺序连续地分散吸收性聚合物和除臭剂,在其上覆盖上层纤维片,然后通过干燥将上层和上层纤维片合结为一体。
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US (1) | US6663949B1 (zh) |
EP (1) | EP1100552B2 (zh) |
JP (1) | JP3587738B2 (zh) |
CN (1) | CN1196502C (zh) |
DE (1) | DE69927824T3 (zh) |
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-
1999
- 1999-07-09 DE DE69927824T patent/DE69927824T3/de not_active Expired - Lifetime
- 1999-07-09 US US09/673,370 patent/US6663949B1/en not_active Expired - Lifetime
- 1999-07-09 EP EP99929774A patent/EP1100552B2/en not_active Expired - Lifetime
- 1999-07-09 CN CN99808986.9A patent/CN1196502C/zh not_active Expired - Lifetime
- 1999-07-09 WO PCT/JP1999/003721 patent/WO2000004938A1/en active IP Right Grant
- 1999-07-09 JP JP19553499A patent/JP3587738B2/ja not_active Expired - Lifetime
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JP2000093459A (ja) | 2000-04-04 |
TW453869B (en) | 2001-09-11 |
JP3587738B2 (ja) | 2004-11-10 |
US6663949B1 (en) | 2003-12-16 |
DE69927824D1 (de) | 2006-03-02 |
WO2000004938A1 (en) | 2000-02-03 |
DE69927824T2 (de) | 2006-04-27 |
EP1100552B1 (en) | 2005-10-19 |
CN1310634A (zh) | 2001-08-29 |
EP1100552B2 (en) | 2009-12-30 |
DE69927824T3 (de) | 2010-07-29 |
EP1100552A1 (en) | 2001-05-23 |
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