CN1072739C - 低温粘合纤维以及由该纤维制造的无纺布 - Google Patents

低温粘合纤维以及由该纤维制造的无纺布 Download PDF

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CN1072739C
CN1072739C CN97113014A CN97113014A CN1072739C CN 1072739 C CN1072739 C CN 1072739C CN 97113014 A CN97113014 A CN 97113014A CN 97113014 A CN97113014 A CN 97113014A CN 1072739 C CN1072739 C CN 1072739C
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fiber
low temperature
nonwoven fabric
temperature adhesion
acid
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CN1168424A (zh
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小岛满
片冈之典
铃木正康
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JNC Corp
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Abstract

本发明的目的是提供一种低温粘合纤维和由该纤维制成的无纺布，该无纺布尽管在低温和高速下热处理仍具有高强度和柔软手感，并具有与热熔粘合剂间的强粘合性，以及提供一种由该无纺布制成的具有吸水性的制品。所述低温粘合纤维其特征在于在聚烯烃复合纤维上涂覆有0.1-2.0%(以纤维的重量计)纤维油剂，该聚烯烃复合纤维具有聚丙烯芯组分和主要含丙烯的烯烃二聚物或三元共聚物的皮组分，其中所述的纤维油剂含有5-15wt%下列组分(A)、5-45wt%下列组分(B)和40-90wt%下列组分(C)的表面活性剂组合物：
(A)至少一种烷基磺酸碱金属盐，
(B)至少一种选自多元醇酯和脂肪酸链烷醇酰胺的化合物，
(C)至少一种选自二元酸酯和聚乙二醇酯的化合物。

Description

低温粘合纤维以及由该 纤维制造的无纺布
本发明涉及低温粘合纤维以及由该纤维制造的无纺布。更具体地，本发明涉及低温粘合聚烯烃复合纤维，该纤维在制备无纺布的工艺中具有低的热处理温度和低的无纺布热封温度以及具有优异的与粘合剂的粘合强度，本发明还涉及由该纤维制连的无纺布。
由于由聚烯烃热粘合复合纤维制造的无纺布具有较好的特性和柔软感和高强度，它们用作卫生材料如卫生巾和尿布。有两种热处理方法可用于从热粘合复合纤维得到无纺布。即，使用抽吸式带烘燥机或抽吸式转筒烘燥机的热空气粘附法，和使用热辊等的热压法。在这些方法中，通过在可得到快速生产速度的相对高温下处理，得到具有高强度的用作卫生材料的无纺布。然而，增加热处理速度虽有助于快速生产无纺布但导致无纺布的强度较低。另一方面，为得到高强度无纺布进行的高温和高压热处理即使使强度增加了，也会使无纺布的手感变硬。
聚烯烃(皮/芯)复合纤维是公知的，例如高密度聚乙烯/聚丙烯(以下简写HDPE/PP)复合纤维、高密度聚乙烯/聚酯(以下简写为HDPE/PET)复合纤维、以及具有丙烯共聚物皮组分和偏心地位于该皮内的聚丙烯芯组分的纤维(日本专利公告No.55-26203，和日本专利申请公开No.2-91217和2-191720)。含有低密度聚乙烯和低分子量聚乙烯的纤维称作热粘合聚烯烃非复合纤维(日本专利申请公开No.63-165511)。
HDPE/PP复合纤维和HDPE/PET复合纤维与其它聚烯烃纤维混合。该混合的纤维用于改善卫生无纺布的特性例如液体渗透性和膨松性。也可使用包括两层互叠在一起的不同纤维构成的纤维网的无纺布。使用这样制成的尿布：即通过用不同种无纺布覆盖在以纸浆等为主体的吸液层的上表面和下表面上、折叠并在中间部分热封而制得。
然而，在混有HDPE/PP复合纤维或HDPE/PET复合纤维的聚烯烃纤维的无纺布中，或者在两层无纺布中，使用具有不同熔点的纤维，这会引起下列缺点：无纺布的强度低、热封部分易撕裂。
当无纺布用作尿布的表面材料时，需要有防水性以防止尿液从裤裆和腰间的皱裥处漏出。在常用的聚烯烃热粘合纤维中，经常使用防水油剂，该防水油剂是通过将具有16-18个碳原子的磷酸烷基酯或石蜡油剂与硅油或氟代烃油混合而得。
当衬料用的无纺布与表层布粘合时，或者无纺布与PE膜粘合时，在裤裆和腰间的皱裥处部分，使用热熔粘合。在使用防水油剂时，无纺布对粘合剂的粘合性差并且封闭处易撕裂。为了避免这种缺点，需要较多的粘合剂。然而，目前需要尿布重量轻、致密并且成本低，因而应提供使用少量热熔粘合剂且具有高粘合性的无纺布。
本发明的目的是提供一种复合纤维，以及由该纤维制成的无纺布，尽管在低温和高速下进行热处理，该无纺布仍具有高的强度和柔软手感。该无纺布具有高的与热熔粘合剂间的粘合性，以及优异的防水性。
本发明人认真地进行了解决上述问题的研究并完成了如下各项发明。(1)、一种低温粘合纤维，其特征在于在聚烯烃复合纤维上涂覆有0.12.0wt％(以纤维的重量计)纤维油剂，该聚烯烃复合纤维具有聚丙烯芯组分和主要含丙烯的烯烃二聚物或三元共聚物的皮组分，其中所述的纤维油剂含有5-15wt％的下列组分(A)、5-45wt％的下列组分(B)和40-90wt％的下列组分(C)的表面活性剂组合物。
(A)至少一种烷基磺酸碱金属盐，
(B)至少一种选自多元醇酯和脂肪酸链烷醇酰胺的化合物，
(C)至少一种选自二元酸酯和聚乙二醇酯的化合物。
(2)、上述(1)所述的低温粘合纤维，其中的主要含丙烯的烯烃二聚物是99-85wt％丙烯和1-15wt％乙烯的共聚物。
(3)、上述(1)所述的低温粘合纤维，其中的主要含丙烯的烯烃二聚物是99-50wt％丙烯和1-50wt％1-丁烯的共聚物。
(4)、上述(1)所述的低温粘合纤维，其中的主要含丙烯的烯烃三元共聚物是84-97wt％丙烯、1-10wt％乙烯和1-15wt％1-丁烯的共聚物。
(5)上述(1)-(4)任一项所述的低温粘合纤维，其中所述的烷基磺酸盐是至少一种选自8-18个碳原子的烷基磺酸与钠或锂的盐的碱金属盐。
(6)、上述(1)-(4)任一项所述的低温粘合纤维，其中的多元醇酯是选自甘油、季戊四醇、山梨醇、脱水山梨醇和蔗糖中至少一种多元醇的酯，并且具有的HLB为5或更小。
(7)上述(1)-(4)任一项所述的低温粘合纤维，其中的脂肪酸链烷醇酰胺是至少一种具有8-22个碳原子的酰基的饱和或不饱和脂族酸的链烷醇酰胺。
(8)上述(1)-(4)任一项所述的低温粘合纤维，其中的二元酸酯是选自己二酸、癸二酸、苯二甲酸、对苯二酸、琥珀酸和马来酸的至少一种二元酸的酯。
(9)、上述(1)-(4)任一项所述的低温粘合纤维，其中的聚乙二醇酯是具有8-18个碳原子的烷基的脂肪酸与分子量为200-80)0的聚乙二醇形成的单酯或二酯中的至少一种。
(10)、由上述(1)-(9)任一项所述的低温粘合纤维制连的无纺布。
(11)、一种具有吸水性的制品，该制品是由上述(10)所述的无纺布制造的。
下面具体说明本发明。
本发明复合纤维的芯组分的聚丙烯是主要含丙烯的晶态聚合物，优选具有约2-150MFR(230℃,2.16kg)的纤维级且熔点约为158℃或更高。这种聚合物通过使用齐格勒-纳塔催化剂的公知的丙烯聚合方法而得到。
本发明复合纤维的主要皮组分共聚物是主要含丙烯的烯烃二聚物(含有99-85wt％丙烯和1-15wt％乙烯)、主要含丙烯的烯烃二聚物(含有99-50wt％丙烯和1-50wt％1-丁烯)、和主要含丙烯的烯烃三元共聚物(含有84-98wt％丙烯和1-10wt％乙烯以及1-15wt％1-丁烯)。该共聚物具有约3-50的MFR(230℃,2.16kg)和约120-158℃或更高的熔点。该共聚物是一种固态共聚物，它是通过使用齐格勒一纳塔催化剂由烯烃共聚得到的，并且基本上是无规共聚物。
当在该共聚物中的共聚单体(乙烯和1-丁烯)的含量小于1wt％时，所得纤维不具有足够的热粘合性。当该共聚物的熔点不在上述范围内时，热封速度、热封强度、无纺布的生产速度、无纺布的强度和无纺布的手感中的任一项指标均降低。
用公知的复合纺丝方法将上述两组分纺成皮芯型或偏心皮芯型纤维、伸张并卷曲。两种复合组分的重量比优选在皮组分/芯组分=20/80-70/30(wt％)范围内。当皮组分含量小于20wt％时，纤维的热粘合性降低，并且在用该纤维制备无纺布时，难以得到具有足够拉伸强度和低温粘合性的由该纤维制成的无纺布。当皮组分含量大于70wt％时，热粘合性足够，但纤维的热收缩性变大，并且该纤维网的尺寸稳定性在无纺布的制造过程中降低。纤维的复合方式优选皮芯同轴方式，因为在热处理时这种方式的纤维网的收缩小。具有0.5-10.0d/f细度和3-60/25mm卷曲数的复合纤维具有良好的梳理加工性，因此是优选使用的。
用于本发明的表面活性剂组合物(A)含有至少一种选自8-18个碳原子的烷基磺酸与钠或锂的盐的烷基磺酸碱金属盐。例如是月桂基磺酸钠、肉豆蔻基磺酸钠、鲸蜡基磺酸钠和硬脂酰基磺酸钠。特别地，具有12-18个碳原子的烷基的盐是优选的。这些盐的混合物也可使用。
用于本发明表面活性剂组合物(B)中的多元醇酯是选自甘油、三羟甲基乙烷、三羟甲基丙烷、季戊四醇、山梨醇、脱水山梨醇和蔗糖中至少一种多元醇的酯，并且HLB值为5或更小。特别地，优选使用甘油一月桂酸酯、甘油一硬脂酸酯、甘油三硬脂酸酯、脱水山梨醇一油酸酯和脱水山梨醇一硬脂酸酯。
用于本发明的表面活性剂组合物(B)中的脂肪酸链烷醇酰胺可用常规酰胺形成方法通过将链烷醇胺如单乙醇胺、二乙醇胺和N-(2-氨基乙基)-乙醇与8-22个碳原子的饱和或不饱和脂肪酸反应而制得。作为链烷醇胺，优选使用二乙醇胺。作为脂肪酸，优选使用具有12-18个碳原子的酸，如月桂酸、肉豆蔻酸、棕榈酸和油酸。
可以使用这些多元醇酯和/或脂族链烷醇酰胺的混合物。
用于本发明表面活性剂组合物(C)中的二元酸酯是选自己二酸、癸二酸、邻苯二甲酸、对苯二酸、琥珀酸和马来酸的至少一种二元酸的酯。特别地，优选使用己二酸二辛酯、癸二酸二丁氧基乙酯和邻苯二甲酸二辛酯。
用于本发明表面活性剂组合物(C)的聚乙二醇酯是分子量为200-800的聚乙二醇与具有8-18个碳原子烷基的脂肪酸的单酯或二酯。特别地，聚乙二醇的分子量优选为200-600，脂肪酸的烷基优选具有12-18个碳原子。例如是聚乙二醇(400)一硬脂酸酯、聚乙二醇(300)二硬脂酸酯、聚乙二醇(400)二硬脂酸酯和聚乙二醇(400)一油酸酯。
可以使用这些二元酸酯和/或聚乙二醇酯的混合物。
用于本发明的纤维油剂是上述表面活性剂组合物(A)(至少一种烷基磺酸盐)、表面活性剂组合物(B)(至少一种选自多元醇酯和脂肪酸链烷醇酰胺的化合物)、和表面活性剂组合物(C)(至少一种选自二元酸酯和聚乙二醇酯的化合物)的混合物，其重量比A/B/C=5-15/545/40-90)％(以总重量为100％计)。
当该纤维油剂的每种组分的重量比不在上述比例范围时，则对低温粘合性、热密封性、与热熔粘合剂的粘合性和防水性中的任一性能有坏的影响。因而难以得到本发明的效果。
在本发明中，将上述纤维油剂涂覆到复合纤维上，涂覆量为0.1-2.0wt％，优选0.3-1.8wt％(以纤维的重量计)。当该纤维油剂的涂覆量小于0.1wt％时，则低温粘合性不充分。当涂覆量大于2.0wt％时，由于卷曲不希望地降低，该复合纤维在梳理加工过程中的可加工性降低。
作为将纤维油剂涂覆到复合纤维上的方法，可使用公知的方法，例如在纺丝工艺中使用接触辊的方法，在纤维伸张工艺中使用接触辊的方法、或者在卷曲工艺后将纤维油剂喷涂在纤维上的方法。
对于本发明的低温粘合纤维，如果需要，可以在该纤维中掺入其它添加剂如热塑性树脂等，或者将其它处理剂涂覆在纤维表面，只要不影响本发明的效果。
本发明的无纺布可按下列步骤制得：将涂覆有纤维油剂的上述复合纤维用梳理机加工成具有所希望单位重量的纤维网，用公知方法加工该纤维网，例如用针刺法、抽吸式烘燥机法或热辊法。当该无纺布用作尿布和卫生巾时，单根纤维的细度优选为0.50-10.0旦(尼尔)，无纺布的单位重量为8-50g/m2是优选的，更优选为10-30g/m2。当单根纤维的细度小于0.5旦时，用梳理机难以得到均匀的纤维网。当单根纤维的细度大于10.0旦时，得到粗糙的无纺布。由这种无纺布制造的表层材料还有不希望的粗糙手感。当单位重量小于10g/m2时，则表层材料太薄以至不能得到足够的强度。当单位重量超过50g/m2时，尽管可以得到优选的强度，但无纺布的手感太粗糙，并且对于实用来说成本太高。
在本发明的无纺布中，如果需要，其它的纤维可与本发明的低温粘合纤维混合使用，只要本发明的优点能够保留。作为其它纤维，例如是聚酯纤维、聚酰胺纤维，聚丙烯纤维、聚乙烯纤维。在该无纺布中，在混有其它纤维的混合物中，本发明纤维的含量应为20％(重量)或更多。当在无纺布中本发明纤维的含量小于20wt％时，则难以得到足够的无纺布的强度和热密封性，并且在很多情况下不能得到良好的与热熔粘合剂的粘合性和防水性。
由下列实施例进一步说明本发明，但并不局限于此。
在实施例中表明的物理数据值由下列方法测定。
纤维油剂量：
使用素格利特萃取器，在回流下用甲醇/石油醚=1/1混合溶剂将10g纤维试样回流萃取3小时，之后蒸发掉溶剂，测定残余物重量。
无纺布强度：
使用包括具有24％粘合面积的轧花辊和平金属辊的热压机，该热压机已加热到一定温度，在线压力为20kg/cm和速度为6m/min条件下热处理梳理机纤维网，则得到单位重量20g/m2的无纺布。机械行走的方向(MD)调整为无纺布的长度方向，垂直于机器行走方向的方向(CD)调整为无纺布的宽度方向。制备长15cm宽5cm的试验片，用拉伸试验机于10cm夹持距离和10cm/min拉伸速度条件下测定拉伸强度。
与热熔粘合剂的粘合性：
使用上述长15cm宽2.5cm的试验片，该试验片是从上述用于测定拉伸强度的无纺布上切下的，将热熔粘合剂以1mm宽涂覆于试验片的轧花侧。20秒后，将另一试验片置于其上，使两试验片的轧花侧相对，并施加2kg/cm2的压力10秒钟，将该试验片置于20℃温度和40％温度恒温槽中24小时。用拉伸试验机于10cm夹持距离和10cm/min拉伸速度条件下测定在与热熔粘合剂结合部分处的断裂强度。用于热熔粘合剂粘合性测定的试验机：由JT Tooshi Co.Ltd．制造，ASM-15型用于涂覆的涂覆器：Noodson 3100型粘合剂：SEBS
防水性：
从上述用于拉伸强度测定的无纺布上切下15cm见方的试验片，依据JISL1092方法A(低水压法)以10cm/min的升降速度测定防水压力(mm)。结果表明，当防水压力越高时，防水性越好。具有50mm或更高的防水压力的无纺布是可以实用的。
热封性：
从上述用于拉伸强度测定的无纺布上切下2.5cm宽的两个试验片。使用一对由相同无纺布制成的两个试验片，或者一对其中一片是上述无纺布制成而另一片是由聚丙烯纤维(2d/f)制成的单位重量为约20g/m2的无纺布制成的试验片，将一片试验片置于另一试验片上并盖住边缘1cm长，在3kg/cm2压力下于一定温度热压3秒钟。用拉伸试验机于10cm夹持距离和10cm/min速度下测量热封边缘的剥离强度。
实施例1-6和对比例1-3
在温度300℃和1000m/min牵引速度下，利用具有直径为0.6mm的喷嘴的复合纺丝装置将具有40/60复合比(皮组分比芯组分)的复合纤维纺丝，该复合纤维中的皮组分是含有5w％1-丁烯和95wt％丙烯的MFR为15的二聚物(A)，芯组分是MFR为10的结晶的聚丙烯(均聚物)，则得到具有4d/f单根纤维细度的皮芯同轴型未拉伸的复合纤维。在纺丝后紧接的卷取工序中，用接触辊将具有表1所示组成的纤维油剂粘附其上。然后，用热辊于95℃将纤维拉伸至原长度的2.4倍。在填塞箱中将纤维卷曲，于95℃温度干燥并切断则得到2d×38mm的复合纤维(实施例1和2)。
在300℃温度和1000m/min送出速度下，利用具有直径为0.6mm的喷嘴的复合纺丝装置将具有40/60复合比(皮组分比芯组分)的复合纤维纺丝，该复合纤维中的皮组分是含有3wt％乙烯/5wt％1-丁烯和92wt％丙烯的MFR为10的三元共聚物(B)，芯组分是MFR为10的结晶的聚丙烯(均聚物)，则得到具有4d/f单根纤维细度的皮芯同轴型未拉伸的复合纤维。在纺丝后紧接的卷取工序中，用接触辊将具有表1所示组成的纤维油剂粘附在其上。然后，用热辊于95℃将纤维拉伸至原长度的2.4倍。在填塞箱中将纤维卷曲，于90℃温度干燥并切断，则得到2d×38mm的各种复合纤维(实施例3-6及对比例1-3)。<无纺布强度>
在20m/min速度用罗拉梳理机将上述纤维梳理则得到单位重量为20g/m2的纤维网。然后将该纤维网经过具有轧花面积为24％的于一定温度和相同速度下的轧花辊，则得到无纺布。
测定无纺布强度并将结果列于表2中。<热熔粘合性试验>
在实施例1-6和对比例1-3的无纺布中，使用于128℃粘合温度得到的无纺布，测定热熔粘合强度，结果列于表2中。<防水性试验>    在实施例1、3和5及对比例2的无纺布中，使用于128℃粘合温度得到的无纺布，测定防水性(水压力)，结果列于表2中。<热封试验1>
在实施例1-6和对比例1-3的无纺布中，将于128℃粘合温度得到的无纺布于130-145℃温度进行热封。这些无纺布的剥离强度列于表3中。<热封试验2>
在实施例1-6和对比例1-3的无纺布中，在135-150℃粘合温度下将于128℃粘合温度得到的无纺布和用纺粘法得到的单位重量为20g/m2聚丙烯无纺布(由Mitsui Sekiyu Kagaku Co.Ltd.制造)热封。剥离强度列于表3中。
用于实施例1-6中的纤维油剂是用于本发明的典型的纤维油剂，其它的表面活性剂组合物(A)、(B)和(C)的化合物具有相似的效果。通过在低温下短时热处理低温粘合纤维可以制得高强度无纺布。由低温粘合纤维制成的无纺布具有良好的与其它聚烯烃无纺布间的热封性，并具有优异的与热熔粘合剂间的粘合强度。由于防水性是50mm或更大，这种无纺布优选地用于如一次性尿布和卫生巾的表面材料领域。
                           表1
纺织用油的组成(w1％)    纺织用油No.     1     2     3     4     5     6
 A 硬脂酰基磺酸钠     10     10     5     10     2     40
 B 甘油三硬脂酸酯脱水山梨醇一月桂酸酯 9 10     35     45 2
二乙醇酰胺月桂酸酯     10     21     10
 C 邻苯二甲酸二辛酯己二酸二辛酯     43     38 32 20     7
PEG(300)二硬脂酸酯PEG(400)二硬脂酸酯 38 32     42     35     36     58
                              表2
共轭纤维     纺织用油     无纺布强度(CD)                g/5cm  热熔粘合剂强度(g)     防水性
芯/皮 纺织用油No.     用量(wt％) 120℃    124℃    128℃  132℃ 耐水压力(mm)
实施例123456对比例123 PP-1/PO-1PP-1/PO-1PP-1/PO-2PP-1/PO-2PP-1/PO-2PP-1/PO-2PP-1/PO-2PP-1/PO-2PP-1/PO-2 123444564 1.001.001.000.201.001.801.001.000.05 52555058045357662015580245 89097098579011501205350330430 138414501384125716501680689750867 166517571730168817902020124013001359 8808908407508701030152220374 77627225
PP-1：聚丙烯(芯成分)PO-1：二聚物(皮成分)PO-2：三元共聚物(皮成分)空白：未进行防水试验
                                表3
    热封试验              1(与相同的无纺布)         g/2.5cm     热封试验                     2(与PP-SB)                  g/2.5cm
 130℃ 135℃ 140℃     145℃  135℃  140℃   145℃  150℃
实施例123456对比例123 220240205185250350906570 9009508809209101230260320230 180019501900185019502300860930867 ＞2800＞2200＞2600＞2600＞2300＞2700165017301800 不不不5080140不不不 120120100165200250不不50 7509058908509801150450340550 175018001850189019502030120010501400
PP-SB：纺粘的聚丙烯无纺布不：未粘结＞：无纺布在热封区域外的区域撕裂。

Claims (11)

1、一种低温粘合纤维，其特征在于在聚烯烃复合纤维上涂覆有以纤维重量计为0.1-2.0重量％的纤维油剂，该聚烯烃复合纤维具有聚丙烯芯组分和主要含丙烯的烯烃二聚物或三元共聚物的皮组分，其中所述的纤维油剂含有5-15wt％的下列组分(A)、5-45wt％的下列组分(B)和40-90wt％的下列组分(C)的表面活性剂组合物：
(A)至少一种烷基磺酸碱金属盐，
(B)至少一种选自多元醇酯和脂肪酸链烷醇酰胺的化合物，
(C)至少一种选自二元酸酯和聚乙二醇酯的化合物。
2、权利要求1的低温粘合纤维，其中的主要含丙烯的烯烃二聚物是99-85wt％丙烯和1-15wt％乙烯的共聚物。
3、权利要求1的低温粘合纤维，其中的主要含丙烯的烯烃二聚物是99-50wt％丙烯和1-50wt％1-丁烯的共聚物。
4、权利要求1的低温粘合纤维，其中的主要含丙烯的烯烃三元共聚物是84-97wt％丙烯、1-10wt％乙烯和1-15wt％1-丁烯的共聚物。
5、权利要求1-4任一项的低温粘合纤维，其中所述的烷基磺酸盐是至少一种选自8-18个碳原子的烷基磺酸与选自钠或锂的至少一种碱金属形成的盐。
6、权利要求1-4任一项的低温粘合纤维，其中的多元醇酯是选自甘油、季戊四醇、山梨醇、脱水山梨醇和蔗糖中至少一种多元醇的酯，并且具有的HLB为5或更小。
7、权利要求1-4任一项的低温粘合纤维，其中的脂肪酸链烷醇酰胺是至少一种具有8-22个碳原子的酰基的饱和或不饱和脂族酸的链烷醇酰胺。
8、权利要求1-4任一项的低温粘合纤维，其中的二元酸酯是选自己二酸、癸二酸、苯二甲酸、对苯二酸、琥珀酸和马来酸的至少一种的二元酸的酯。
9、权利要求1-4任一项的低温粘合纤维，其中的聚乙二醇酯是具有8-18个碳原子的烷基的脂肪酸与分子量为200-800的聚乙二醇形成的单酯或二酯中的至少一种。
10、使用权利要求1-4任一项的低温粘合纤维制造的无纺布。
11、一种具有吸水性的制品，该制品是使用权利要求10的无纺布制造的。
CN97113014A 1996-04-17 1997-04-16 低温粘合纤维以及由该纤维制造的无纺布 Expired - Fee Related CN1072739C (zh)

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KR19980032083A (ko) 1998-07-25
CN1168424A (zh) 1997-12-24

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