CN101151406B - 热粘合的无纺织物 - Google Patents

热粘合的无纺织物 Download PDF

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CN101151406B
CN101151406B CN2006800108433A CN200680010843A CN101151406B CN 101151406 B CN101151406 B CN 101151406B CN 2006800108433 A CN2006800108433 A CN 2006800108433A CN 200680010843 A CN200680010843 A CN 200680010843A CN 101151406 B CN101151406 B CN 101151406B
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A·格赖纳
K·维瑟尔
H·席林
G·弗雷
R·伯克曼
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Abstract

本发明涉及一种热粘合的无纺织物，所述无纺织物包含低收缩性的芯-皮双组分纤维，其中，所述低收缩性的芯-皮双组分纤维由结晶的聚酯芯部和熔点低至少10℃的结晶的聚酯皮组成，并在170℃具有小于10％的热收缩率。

Description

热粘合的无纺织物
技术领域
本发明涉及一种用于具有改善的热和化学稳定性的热粘合/结合(binden)无纺织物。本发明还涉及所述无纺织物的一种应用。
背景技术
由文件EP0340982B1已知可熔融粘合的纤维和由这种纤维制成的无纺织物。可熔融粘合的纤维是双组分纤维，所述双组分纤维包括一种至少部分结晶的第一聚合物组分和粘附在第一组分的表面上的第二组分，所述第二组分具有聚合物的兼容的混合物，所述混合物包括至少一种无定形聚合物和至少一种至少部分结晶的聚合物。所述第二组分的熔点应至少在第一组分以下30℃，但至少等于或大于130℃。此外第二组分的无定形聚合物和第二组分的至少部分结晶的聚合物的重量比在15∶85至90∶10的范围内，并且这样来确定所述重量比，即防止所述双组分纤维与类似的双组分纤维的结合，并且第一组分形成一种按皮芯构型的形式纺制的双组分纤维的芯部，而第二组分形成其皮部。这种双组分纤维与传统的聚酯纤维相混合并热粘合成无纺织物，通过施加研磨剂微粒将所述无纺织物加工成研磨布。
由文件JP07-034326已知可热粘合的组合纤维(Konjugatfaser)，所述组合纤维具有皮芯结构，其芯部由聚酯组成，所述聚酯包含聚对苯二甲酸乙二醇酯(PET)作为主组分，其皮部由共聚的聚酯或并排(side-by-side)组合纤维制成，所述组合纤维由聚对苯二甲酸乙二醇酯或共聚的聚酯组成。所述共聚的聚酯构成熔点较低的组分并包含对苯二甲酸丁二醇酯单元和间苯二甲酸丁二醇酯单元作为循环/复现的结构单元。由这种双组分纤维制成的无纺织物应具有非常好的耐热性并且相对于压力载荷具有防疲劳的特性，从而这种无纺织物可以特别是在汽车领域用作聚氨酯座垫的替代材料。
此外，还存在由包括未拉伸和拉伸的PET纤维的混合物制造热粘合无纺织物的可能性。但对于这种无纺织物，必须在热和压力的作用下在轧光机内进行粘合。如果还存在可结晶的成分，未拉伸的无定形PET纤维的可粘合性不是基于熔融过程，而是基于PET的在90℃以上开始的结晶过程所述结晶过程。这种无纺织物具有非常令人满意的化学和热稳定性。但其制造过程只允许由很小的灵活性。例如对于未拉伸的PET纤维，无法多次激活其可粘合性，因为可粘合性是基于在熔点之下的不可逆过程存在的。对于具有大于150g/m2的面密度和未拉伸PET纤维的无纺织物，完全粘合也是困难的，因为在轧光过程中不能使热量从外进入无纺布带的内部足够远。总是会出现程度不等的梯度。
发明内容
本发明的目的是，提供一种热粘合的无纺织物，这种无纺织物在其热稳定性上，特别是在所获得的无纺织物的收缩倾向上具有改善的特性。此外，与包含由单体混合物例如间苯二甲酸/对苯二甲酸的组成(混合)共聚物的纤维相比，还提高化学稳定性。
根据本发明，所述目的通过一种热塑性粘合的无纺织物来实现，所述无纺织物包含低收缩性的芯-皮双组分纤维。所述低收缩性的芯-皮双组分纤维由结晶的聚酯芯部和熔点低至少10℃的结晶的聚酯皮部组成，并在170℃具有小于10％、特别是小于5％的热空气收缩率。相应的无纺织物在150℃(1小时)的温度载荷下具有小于2％的热尺寸改变(收缩和膨化/膨胀(Bausch))。在本发明的范围内，结晶(体)理解为这样一种聚酯聚合物，所述聚酯聚合物具有＞40焦耳(J)/g的熔化焓(DSC)，并且在＜10℃/min时其熔化峰值的宽度下降 
Figure DEST_PATH_GA20192549200680010843301D00011
低收缩性的双组分纤维的皮部由均质的、由单体对制成的聚酯聚合物组成，所述聚酯聚合物的＞95％只由聚合物对形成。对于本文所述的聚酯的 情况，这意味着，所述聚合物的＞95％由唯一一种二羧酸和唯一一种二元醇(Dialkohol)组成。
芯组分和皮组分的质量比通常为50∶50，但在特殊的应用领域可以在90∶10和10∶90之间变化。
特别优选的是这样一种无纺织物，其中所述低收缩性的芯-皮双组分纤维的皮由聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTT)或聚对苯二甲酸乙二醇酯(PET)组成。
此外优选这样一种无纺织物，其中所述低收缩性的芯-皮双组分纤维的芯部由聚对苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯(PEN)组成。
除了低收缩性的芯-皮双组分纤维以外，根据本发明的无纺织物根据相应的应用场合还可以包括其它纤维。优选和低收缩性的双组分纤维一起采用0至90％重量百分比的例如单丝的标准聚酯纤维。
根据本发明的无纺织物优选由具有在0.1至15dtex之间的范围内的纤度的低收缩性的芯-皮双组分纤维组成。根据本发明的无纺织物具有20至500g/m2之间的面密度。根据本发明的无纺织物在例如150-190g/m2的面密度下可实现大于1Nmm的、按ISO2493确定的、横向于机器运行方向的弯曲刚度。
用于制造热粘合的无纺布的方法在于，将纤维铺放成无纺织物，进行热粘合，并在必要时紧接着进行致密化。在该方法中，根据本发明的无纺织物的纤维在一热熔化炉中停留，所述热熔化炉使得可以对粘合纤维进行均匀的调温处理。低收缩性的芯-皮双组分纤维优选按纸铺放(Papierlege)法湿式铺放，并进行干燥，或按梳理(Kardier)法或气流成网(Airlaid)法干式铺放，并接着在200至270℃的温度下进行粘合，并可选地通过轧光机或挤压设备进行致密化，所述设备具有低于皮聚合物的熔点的，优选＜170℃的辊温度。优选直接在干燥机中的粘合过程之后对仍较热的纤维进行所述致密化。
所获得的热粘合无纺织物具有在＜2％，优选＜1％范围内的收缩值或膨化值。
由于其高的热稳定性、小的收缩倾向和化学变化稳定性，根据本发明的无纺织物适于用作液体过滤介质、薄膜支承无纺布(Membranstützvlies)、气体过滤介质或用于复合材料表面的无纺织物。尤其是特别适于用作用于机动车辆的发动机中的油过滤介质。
附图说明
下面借助于附图详细说明本发明。其中
图1示出一图线，在该图线中无纺织物A和B的最高拉力用作在空气和油中存放后相应新状态的指数(DIN53508和DIN53521)；
图2示出一图线，在该图线中无纺织物A和B的最高拉力用作在150℃在空气和油中存放后相应新状态的指数(DIN53508和DIN53521)；
图3示出一图线，在该图线中，无纺织物A和B在不同的温度下的最高压力用作相应新状态的指数(DIN EN 29073-03)；
图4示出薄膜支承无纺布的电子显微照片，所述无纺织物与未拉伸的聚酯纤维粘合(无纺织物E；对比示例)；
图5示出薄膜支承无纺布的电子显微照片，所述无纺织物根据本发明100％由低收缩性的PET/PBT双组分纤维组成(无纺织物F)；
图6示出具有结晶皮部聚合物(这里PET/PBT；本发明)的双组分纤维A的DSC-曲线；
图7示出具有无定形皮聚合物(这里PET/CoPET；现有技术)的双组分纤维B的DSC-曲线
具体实施方式
测试方法
弯曲刚度
弯曲刚度按ISO2493确定。
热尺寸变化(收缩)
在纵向和横向上给试样(DIN A4-尺寸样品)设置标记，所述标记具有200mm的间距。将试样在循环空气烘箱(Umluftofen)中在150℃存放1小时并接着在室温下冷却20分钟后，确定尺寸变化。对于纵向和横向，所述尺寸变化分别相对于初始值用百分数给出。百分数前面的符号给出尺寸变化是正(+)或是负(-)。由至少六个单值(测量)形成平均值。
尺寸变化(膨化)
在纵向和横向上给试样(DIN A4-尺寸样品)设置标记，在所述标记处按ISO 9073/2确定厚度。将试样在循环空气烘箱中在150℃存放1小时并接着在室温下冷却20分钟后，在标记处重新确定厚度(ISO 9073/2)。用百分数给出膨化率(B)并如下式计算膨化：
B[％]＝(存放后的厚度×100/存放前的厚度)-100
由至少六个单值(测量)形成平均值。
热空气收缩率的测试
对20个单根纤维进行测试。给所述纤维设置如下面所述的预紧重物。在夹紧板的夹紧部中夹紧自由的纤维端。确定夹紧的纤维的长度(L1)。接着，在没有重物的情况下自由悬垂地将纤维在170℃在循环空气干燥箱中调温10分钟。在室温下冷却至少20分钟后，将与测量L1中的相同重物重新悬挂到纤维上，并测量收缩过程后新的长度(L2)。由下式计算用百分数表示的热空气收缩率：
HS[％]＝(∑L1-∑L2)＊100/∑L1
预张紧重量的大小
  纤度[dtex]   预紧重物[mg]   纤度[dtex]   预紧重物[mg]
  最高1.20   100   5.40以上至8.00   350
  1.20以上至1.60   100   8.00以上至12.00   500
  1.60以上至2.40   150   12.00以上至16.00   700
  2.40以上至3.60   200   16.00以上至24.00   1000
  3.60以上至5.40   250   24.00以上至36.00   1500
在自由悬垂状态，纤维应表现为去卷曲。如果卷曲变形过于强烈，则 选择下一个较重的重物。
熔化焓(DSC)
在Mettler Toledo公司的DSC装置中对试样进行称重，并利用以从0℃至300℃、10℃/min的温度程序对其进行加热。吸热的熔融峰值下方的面积与纤维的初始重量和与此相关的皮和芯组分的质量相结合以J/g表示相应组分的熔化焓。
实施例1
无纺织物A是一种具有190g/m2的面密度的、干式铺放的、经梳理的并热粘合的无纺织物。所述无纺织物的75％由低收缩性的、皮熔点为225℃并且芯-皮比例为50∶50的PET/PBT双组分纤维组成，该无纺织物的25％由常见的PET纤维组成。厚度为0.9mm，而透气性在200Pa为850l/m2s。所述纤维中140g/m2通过具有交叉铺网机(Querleger)的梳理机(Krempel)进行梳理，其余的50g/m2纵向铺放地进行梳理。在热熔化炉中在约240℃下使所述无纺织物粘合，并利用出口压力机将其校正到目标厚度。
对比示例
与无纺织物A类似地制造无纺织物B。区别之处在于使用具有约200℃的皮熔点的常见PET/Co-PET双组分纤维并将炉温降低到230℃。所得到的面密度、厚度和透气性是相同的。
与无纺织物B相比，根据本发明的无纺织物A的优点在下面说明：
●对于无纺织物A，在干燥器之后，无纺织物的宽度只降低约9％，相反对于无纺织物B出现约21％宽度损失。
●无纺织物A横向的弯曲刚度高15％。
●对于无纺织物A，在150℃下存放之后厚度增加(热尺寸变化)1.5％，对于无纺织物B为4.7％。
●对于无纺织物A，在150℃下在空气和油中存放之后，热和化学稳定性明显改善(图1和2)。对于在发动机油中存放时，图线示出无纺织物B明显较强烈的破坏。图3中的下降部指示了无纺织物B的化学稳定性问题。
●对于无纺织物A，在各种不同温度下的最高拉力示出明显较为有利的变化分布(图3)。
实施例2
无纺织物C和D是湿式铺放的、已干燥的以及热粘合的、具有198g/m2 和182g/m2的面密度的无纺织物。所述无纺织物的72％由低收缩性的具有225℃的皮熔点和50∶50的芯-皮比例的PET/PBT双组分纤维组成，所述无纺织物的28％由常见的PET纤维组成。所述纤维作为分散的切段短纤维存在。按纸铺放法将所述纤维铺放在筛网带上，对其进行干燥并在一第二干燥器中使其热粘合。所述无纺织物突出的特性在于非常好的机械测试值以及其非常好的收缩特性(表2)。在这种情况下不可能与由传统的具有CoPET皮的双组分纤维制成的无纺织物进行比较，因为这种纤维由于其高收缩值到目前为止还不能应用到所述无纺织物设备上，或者说这种纤维具有至少20％的宽度损失。根据本发明的湿式无纺织物具有约3％的宽度损失。
表2无纺织物C和D的测试值
  无纺织物C   无纺织物D
  面密度   198g/m2   182g/m2
  厚度   1.10mm   0.99mm
  透气性   714l/m2s   796l/m2s
  纵向最高拉力   536N/5cm   446N/5cm
  横向最高拉力   358N/5cm   329N/5cm
  纵向弯曲刚度   2.5Nmm   1.9Nmm
  横向弯曲刚度   2.1Nmm   1.6Nmm
  纵向收缩率150℃，1小时   0.0％   0.3％
  横向收缩率150℃，1小时   0.0％   0.0％
  膨化率150℃，1小时   0.7％   1.5％
特别是在用于具有分离的、用于脱水和用于热熔合的干燥机的湿式铺放过程中时，根据本发明的低收缩性双组分无纺织物提供了优点，因为所 述纤维与未拉伸的粘合纤维相比可以多次激活，或者说在第一次干燥过程中没有完全反应。
根据本发明的无纺织物A、C、D特别适于用作机动车辆中的发动机油过滤介质。
例3
现有技术中的由包括拉伸和未拉伸的单丝PET纤维组成的轧光PET无纺织物(对比示例；无纺织物E)用作薄膜支承无纺织物。特别是对于具有＞150g/m2的面密度的较重的无纺织物，由于轧光过程存在表面封闭( )的危险，因为为了实现无纺织物良好的完全粘合，高的辊温度或缓慢的制造速度是必需的，以使必要的热量进入无纺织物的内部。封闭的表面隐含了形成膜的危险，这种危险又导致不佳的薄膜附着性和小的通流率(无纺织物E)。图4和5示出常用的无纺织物(对比示例；无纺织物E；图4)的不同的表面和根据本发明的无纺织物(无纺织物F；图5)的表面。
在两种无纺织物的测试值的比较中也可以看出在无纺织物F(图5)中完全不存在表面封闭。这样，在其它测试数值相当时，无纺织物F的空气透过性提高了一个数量级(表3)。
表3：无纺织物E和F的测试值
  无纺织物E   无纺织物F
 面密度   190g/m2   190g/m2
 厚度   0.26mm   0.25mm
 空气透过性(200Pa)   5l/m2s   41l/m2s
 纵向最高拉力   520N/5cm   514N/5cm
 横向最高拉力   470N/5cm   560N/5cm
在皮部中具有共聚物的传统双组分纤维由于高的收缩值和由此引起的重量波动以及由于皮聚合物通常得不到食品卫生许可而不能用于这个领域。根据本发明的由相应双组分纤维组成的无纺织物克服了上述两个障碍，因为所述无纺织物是低收缩性的并由于均聚物的结构可以毫无问题地得到 食品卫生许可(Lebensmittelzulassung)。
实施例4
为了进一步说明根据本发明的无纺织物与具有包括基于共聚物的皮部的双组分纤维的传统无纺织物的区别，在图6和7中对比具有结晶的皮部聚合物的纤维(纤维A；这里是PBT)的DSC曲线(差示热量扫描法(differential scanning calorimetry))和传统双组分纤维(纤维A；这里是CoPET)的DSC曲线。在对低熔点组分的熔化焓的分析中证明，纤维B的皮部具有明显低于纤维A的熔化焓，熔化焓用J/g表示。
熔化焓是(衡量)聚合物中结晶比例的直接的尺度。两种纤维的芯-皮比例都为1∶1，由此得到以下纤维皮部的熔化焓：
纤维A 63J/g
纤维B 29J/g
这里两种纤维的芯部可以用作测量基准，对两种纤维，所述芯都是由PET组成。所得到的熔化焓的值相当(59J/g对54J/g)。
与测量值无关，在DSC曲线的对比中，基于共聚物(这里是CoPET)的纤维皮部的特征是低峰值高度和较宽的峰值基底(Peakbasis)。通过在聚对苯二甲酸乙二醇酯中嵌入共聚用单体，例如间苯二甲酸，可以降低聚合物的熔点以及结晶度或者说可结晶性。
因此根据本发明的无纺织物基于纤维A类型的纤维。

Claims (16)

1.一种热粘合的无纺织物，所述无纺织物包含低收缩性的芯-皮双组分纤维，其中，所述低收缩性的芯-皮双组分纤维由结晶的聚酯芯部和熔点低至少10℃的结晶的聚酯皮组成，并在170℃具有小于10％的热收缩率。
2.按权利要求1的无纺织物，其特征在于，所述低收缩性的双组分纤维的皮部＞95％由均质的聚酯聚合物组成，所述聚酯聚合物不是共聚物。
3.按权利要求2的无纺织物，其特征在于，所述低收缩性的芯-皮双组分纤维的皮部由聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯或聚对苯二甲酸乙二醇酯组成。
4.按权利要求1的无纺织物，其特征在于，所述低收缩性的芯-皮双组分纤维的芯部由聚对苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯组成。
5.按权利要求1至4中任一项的无纺织物，其特征在于，所述低收缩性的芯-皮双组分纤维具有在0.1至15dtex之间的纤度。
6.按权利要求1至4中任一项的无纺织物，其特征在于，所述低收缩性的芯-皮双组分纤维的芯组分和皮组分的质量比在10∶90和90∶10之间。
7.按权利要求1至4中任一项的无纺织物，其特征在于，所述低收缩性的芯-皮双组分纤维的芯组分和皮组分的质量比为50∶50。
8.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物包括最高90％重量百分比的一种或多种其它纤维。
9.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物是湿式铺放的。
10.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物是干式铺放的。
11.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物具有20至500g/m2之间的面密度。
12.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物在＞150g/m2的面密度下具有大于1Nmm的横向弯曲刚度。
13.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物在150℃下1小时后具有＜2％的热尺寸变化。
14.按权利要求1至4中任一项的无纺织物，其特征在于，所述无纺织物在150℃下1小时后具有＜1％的热尺寸变化。
15.按权利要求1至14中任一项的无纺织物作为液体过滤介质、薄膜支承无纺织物、气体过滤介质、蓄电池隔片或用于复合材料表面的无纺织物的应用。
16.无纺织物按权利要求15的应用，其特征在于，用作用于机动车辆发动机的油过滤介质。
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PL1866469T3 (pl) 2013-12-31
KR100942879B1 (ko) 2010-02-17
DE102005015550A1 (de) 2006-10-26
DE102005015550C5 (de) 2013-02-07
WO2006105836A1 (de) 2006-10-12
US8124550B2 (en) 2012-02-28
US20120129032A1 (en) 2012-05-24
DE102005015550B4 (de) 2009-07-23
US8481437B2 (en) 2013-07-09
EP1866469B1 (de) 2013-07-17
DK1866469T3 (da) 2013-10-14
EP1866469A1 (de) 2007-12-19

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