CN1205042A - 吸收性纤维素材料及其生产 - Google Patents

吸收性纤维素材料及其生产 Download PDF

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CN1205042A
CN1205042A CN97191331A CN97191331A CN1205042A CN 1205042 A CN1205042 A CN 1205042A CN 97191331 A CN97191331 A CN 97191331A CN 97191331 A CN97191331 A CN 97191331A CN 1205042 A CN1205042 A CN 1205042A
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fine hair
hydrophobic substance
fiber
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absorbing material
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I·提伯林
S·瓦荷伦
E·林德格伦
K·马勒穆伯格
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Nouryon Pulp and Performance Chemicals AB
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Abstract

本发明涉及将纤维素纤维撕碎成为绒毛的方法,其中在撕碎前在水的存在下用比表面积至少约为50m2/g的疏水物质处理纤维以改进其吸着能力;也涉及由此方法制得的绒毛和由这种绒毛制得的吸收制品;所述疏水物质在改进包含纤维的吸收材料的吸着能力中的应用;以及生产吸收材料的方法,该材料是用这种纤维浆页经撕碎得到的,纤维在撕碎前已在水的存在下用所说类型的疏水物质进行处理以改进其吸着能力;还涉及用这种方法制得的吸收材料。

Description

吸收性纤维素材料及其生产
本发明涉及具有改进的吸着能力的绒毛的生产方法和可由此方法生产的绒毛。本发明也涉及用比表面积大于50m2/g的疏水物质处理纤维素纤维以改进由此纤维组成的吸收材料的吸着能力的应用。本发明还涉及由撕碎或弄松纤维素桨页得到的纤维素纤维组成的吸收材料的生产方法,吸收材料的结构具有改进的吸着能力。
在本文中,“吸着能力”的概念指吸收材料吸取诸如水或水溶液之类的液体(包括诸如尿、血和经液之类的体液)的吸收率,或者是指吸收材料的液体滞留能力,或同时指这两种特征。其吸着机理可为吸附或吸收或二者的结合。
如“Pulp and Paper Manufacture(纸浆和纸的制备)”(Vol.2,pp 280-281,Joint Textbook Committee of the Paper Industry,1987,在此提出供参考)中所述,绒毛一词用于以机械方法从干浆分离的纤维,这种纤维应用于家庭或卫生领域中的干法成形的非织造纤维幅或垫。从此参考文献可以明显地看到,在这些领域中使用时,绒毛的吸液率和持液能力都是很重要的。这对于诸如例假用品之类的吸收制品(例如卫生巾、内裤衬里、止血栓塞等)、尿布、绷带、成人失禁服等是特别有效的。好的吸液率和持液能力是这种制品功能的明显的先决条件。但是在使用时,这种制品持久性地受到穿戴者的体重和运动给予的压力,因此有足够高的持液能力能使其在压力下也能保留住被吸收的液体是很重要的。再者,为使穿戴者有好的舒适感,制品应提供干爽(即应避免制品再弄湿穿戴者的皮肤)的感觉,所以对持液能力提出了甚至更高的要求。通常是使用某些与水接触时形成水凝胶的聚合材料(被称为“超吸收剂”)来提高这类制品的吸着能力,然而虽然制品的能力提高了,但因液体是与超吸收剂颗粒结合的,构成绒毛的纤维素纤维本身的吸着能力事实上并未因使用这种超吸收剂而得到提高。
本发明要解决的问题就是提供一种吸着能力改进了的绒毛的生产方法。
该问题由所附权利要求中所限定的方法得到解决。
所述类型的疏水性物质能给予改进的吸收特性的原因至今尚未清楚地确立。
在本发明方法中,纤维素纤维页是被撕碎成为绒毛的。本文中的“页”意指页或幅。页(下称“纤维浆页(pulp sheet))”的形成可用本技术领域中已知的形成方法之一,例如类似于常规造纸中的湿法,或闪干法,两种方法均叙述于下述文献中:Pulp and Papermanufacture(纸浆和纸的制造)Vol.1,pp753-757,JointExecutive Comittee of Vocational Education Comittee of thePaper Industry,1969。在此提供参考。
用疏水性物质“处理”纤维意指使该物质的颗粒处于纤维附近或与纤维接触,最好是使颗粒保持在纤维附近或与纤维接触至少约1分钟,适合的是至少约30秒,特别是至少5秒。可以在过程中的任何点上进行处理,该过程始于纤维的互相分离,终于纤维浆页的干撕碎。但最好在纤维干物质含量至少约为25%、适合的至少约为35%,最优选至少约50%时进行处理。
按如下所述改良的DIN 66131标准方法测定的疏水物质颗粒的比表面积至少约为50m2/g,优选至少约为100m2/g,最优选至少约为1000m2/g。
疏水性物质可以是任何基本上不溶于水的物质,最好具有不高于约1g/100g水的溶解度,适合的不高于0.1g/100g水,只要它具有上述的比表面积即可。有用的疏水性物质的例子是活性炭、疏水沸石和聚四氟乙烯(即泰氟隆)。疏水性物质最好是多孔的。在一最佳具体实施方案中,疏水性物质是疏水性低于约0.99%、优选低于约0.90%、适合的是低于0.70%(重量)的残留丁醇的活性炭或沸石(用下述的残留丁醇测试法测定)。特别优选的沸石是SiO2/Al2O3摩尔关系至少为5的沸石。
虽然疏水物质可以干态和湿态加入纤维,但最好是将其包括在一水混合物中,通常是成为分散液或淤浆。将混合物方便地喷涂在形成的纤维浆页上是适合的,加入物质的适合量约为0.1-10、优选约0.5-5公斤/公吨干浆。也可选择地当纤维被悬浮在水溶液中(例如在成页以前的纤维浆生产过程的原料中)时进行处理,疏水物质在原料中的适合量约为0.1-10,优选约0.5-5公斤/公吨干浆。
处理可以在滞留剂存在下进行以确保有足够的物质颗粒保持与纤维接触或在纤维附近足够长的时间以产生所要求的效果。优选的滞留剂的例子是多糖,诸如淀粉、纤维素衍生物、呫吨胶(xanthangum)和瓜尔胶;以及合成的均聚物,诸如聚丙烯酰胺(PAM)、聚酰胺胺(PAA)、聚二烯丙基二甲基氯化铵(聚DADMAC)、聚乙烯亚胺(PEI)和聚氧乙烯(PEO)或它们的共聚物。
虽然此物质可保留在撕碎后的绒毛里,但这并不被认为是本发明的主要点。事实上,在撕碎后的绒毛里用于处理的物质即使低于约65%,低于30%或甚至少到约1%,当与从未处理的纤维浆生产的绒毛相比时,其吸收效果是十分显著地提高了。但在一些例子中让大量的物质存留在绒毛中可能是有利的,例如在US-A-4,826,497和WO 91/11977中公开的当该物质是给吸收制品(例如尿布和例假用品)提供除臭特征的疏水性沸石时。但应当注意的是文献中的沸石是以与绒毛分离的状况或与撕碎后的绒毛混合的状况使用的。
本发明也涉及用本发明方法制备的绒毛。从下面的实施例可知,当与现有技术混合有沸石或活性炭的绒毛(即在撕碎后)比较时,这种绒毛显现了特别好的吸收特性。其效果提高的原因尚不知道,但这显然是由于特定的应用方法给予绒毛某种特性所致。
本发明也涉及用这类疏水物质处理纤维素纤维以改进由纤维组成的吸收材料,诸如绒毛或卫生纸(例如软纸)的吸着能力的应用。本发明还涉及吸收材料的生产方法,包括例如干法成形非织造物或薄纸的生产方法,该方法包括如上所述在形成绒毛前用疏水物质处理纤维素纤维。本发明也涉及吸收制品,诸如卫生巾、内裤衬里、止血栓塞、尿布、绷带、成人失禁服等,其中使用了由本发明方法制备的绒毛。
构成纤维浆页的纤维通常是将木材(一般是碎片)崩解成纤维或纤维束得到的。在本文中“纤维束”的概念与“纤维”的概念相等。分离的纤维可用技术人员知道的任何制浆法制取,例如用生产机制浆(MP)、石磨木浆(SGW)、压磨木浆(PGW)、精机制浆(RMP)、热机制浆(TMP)、化学机制浆(CMP)或化学热机制浆(CTMP)的方法。虽然优选的是化学浆,诸如硫酸盐和亚硫酸盐浆,但纤维素纤维为棉纤维也是有利的。另一似乎可能的纤维源是废纸再生纤维。
本发明将用下列的实施例进行更详尽的说明。所示的“份”和“百分数”是指重量,除非另外指明。在实施例中使用了表I中给予的疏水物质,其中疏水物质A-N为沸石,O为活性炭。
    表Ⅰ
疏水物质   疏水性,%   SiO2/Al2O3摩尔关系     类型
    A     0.03     900     ZSM-5
    B     0.14     35     ZSM-5
    C     0.15     35     ZSM-5
    D     0.24     29     Y
    E     0.27     25     Y
    F     0.28     29     Y
    G     0.30     5.1     Y
    H     0.46     12     Y
    I     0.81     5.2     Y
    J     0.81     5.2     Y
    K     0.83     5.5     Y
    L     0.99     2.6     X
    M     0.99      2     A
    N     0.99      2     A
    O   活性炭
表中所示的沸石的疏水性是用所谓的残留丁醇测试法(见GB2,014,970所述)测定的。在此测试法中,沸石是在空气中于300℃下加热16小时进行活化的。然后将10重量份的这种活化了的沸石与1重量份丁醇-1和100重量份水组成的溶液相混合。将得到的淤浆在25℃下缓慢搅动16小时。最后测定溶液中的丁醇-1残留含量并以重量百分数表示。因而残留含量低即表示疏水性程度高。
活性炭是多孔炭类的集合名词,它们是用气体处理炭或用碳质原料的碳化同时用化学处理进行活化制备的。活性炭的较详细的叙述见于“Ullmann's encyclopedia of Industrial Chemistry(乌尔曼工业化学大全)”Vol.A 5,P124ff.,1986,在此提供参考。
比表面积是用基于DIN 66131(1993年7月)的所谓BET法测定的。此方法中的面积是用在相对压力P/P0为0.03时吸收等温曲线上的一点测定的。P为该方法中被吸收气体的压力;P0为相同气体的饱和蒸气压。活性炭的比表面积约为1000m2/g;ZSM-5型和A型沸石约为500m2/g;沸石-X和沸石-Y各为约800m2/g。
在下面的实施例中,制得的绒毛进行了再湿性试验,其中一些实施例也进行了吸收率试验。吸收率测定的试验法是用SCAN-C33∶80,该方法是将直径为50mm的3克绒毛样品竖直放置,在其顶上加500克重量。让样品由下端吸水,用电子检测器自动测定水渗透至样品上表面所需的时间。水渗透至上表面所需的时间愈短,绒毛的吸收率愈高。测定再湿性或持液能力的试验方法是将直径为50mm的3克绒毛竖直放置,在其顶上加1公斤重量30秒钟,然后解除重量。向样品加10毫升水,为时10秒钟,并让液体沥出样品30秒钟。此后样品再负重1公斤4分钟。将15张8×8cm的滤纸置于样品顶端,此样品加滤纸的组合体上加以5公斤重量1分钟,此后称量15张滤纸。滤纸由于再湿性而有重量的增加。增加的重量少指明其再湿性低。
实施例1-14
将10克硫酸盐纸浆于一实验室碎浆机中以500毫升水打浆10分钟。得到的浆料通过网笼滤布脱水,得到直径为210mm的纤维浆页。除实施例1外,将含0.2%疏水物质的15克水溶液喷于各实施例中的纤维页上,实施例1是对比实施例。各浆页所加的疏水物质量相当于3公斤物质/吨干浆。将浆页于60℃干燥120分钟,然后在锤头粉碎机中撕碎成为绒毛。将绒毛形成三个样品,每个3克。在23℃和50%RH的环境条件下将制得的绒毛样品进行再湿性试验,见下表II。
                              表Ⅱ
                           硫酸盐浆,3Kg疏水物质/吨浆
    用喷雾法加疏水物质
  疏水物质   实施例     再湿性(g)
    参考     1     5.0
    A     2     4.5
    B     3     4.2
    C     4     4.4
    D     5     4.0
    F     6     3.2
    G     7     3.8
    H     8     4.1
    I     9     4.2
    J     10     4.7
    L     11     4.5
    M     12     4.1
    N     13     4.4
    O     14     4.4
很明显,按本发明方法生产的绒毛比未经处理的绒毛有更好液体保留能力。
实施例15-21
重复实施例1-14的步骤,但在打浆时加入疏水物质而不用喷雾法。实施例15是对比实施例,即不加任何疏水物质。将制得的绒毛样品进行再湿性试验,见下表III所述。
表III
硫酸盐浆,3公斤疏水物质/吨浆
用喷雾法加疏水物质
疏水物质 实施例 再湿性(g)
参考 15 5.0
B 16 4.8
C 17 4.5
D 18 4.5
F 19 4.6
G 20 4.2
I 21 4.7
显然,按本发明方法生产的绒毛比未经处理的绒毛有更好的液体保留能力。
实施例22-26
重复实施例1-14的步骤,但使用的是亚硫酸盐浆。实施例22是未加疏水物质的对比实施例。结果示于下表IV中。
表IV
亚硫酸盐浆,3公斤疏水物质/吨浆
用喷雾法加疏水物质
疏水物质 实施例 再湿性(g)
参考 22 5.15
C 23 4.37
F 24 4.22
L 25 4.84
N 26 4.55
显然,按本发明方法生产的绒毛比未经处理的绒毛有更好的液体保留能力。
实施例27-29
重复实施例1-14的步骤,但使用的是化学热机制浆(CTMP),也测定了吸收率。实施例27是未加疏水物质的对比实施例。结果示于下表V中。
表V
CTMP,3公斤疏水物质/吨浆
用喷雾法加疏水物质
疏水物质 实施例 吸收率,s 再湿性,g
参考 27 12 5.00
C 28 11 4.32
F 29 8.2 4.41
显然,按本发明方法生产的绒毛比未经处理的绒毛有更快的吸收率和更好的液体保留能力。
实施例30-32
重复实施例1-14的步骤,但使用的是棉花,也测定了吸收率。实施例30是未加疏水物质的对比实施例,结果示于下表VI中。
表VI
棉纤维,3公斤疏水物质/吨浆
用喷雾法加疏水物质
疏水物质 实施例 吸收率,s 再湿性,g
参考 30 5.1 6.54
C 31 4.6 6.24
F 32 4.4 6.00
显然,按本发明方法生产的绒毛比未经处理的绒毛有更快的吸收率和更好的液体保留能力。
实施例33-38
重复实施例1-14的步骤,但在测定再湿性的试验方法中使用了一种水溶液,其与试验有关的性质类似于血的性质。此水溶液含10克/升NaCl、80克/升甘油、4克/升NaHCO3;溶液的粘度用羧甲基纤维素(CMC)调至约12cPs(厘泊),表面张力用非离子表面活性剂调至约50mN/m。实施例33是未加疏水物质的对比实施例。结果示于下表VII中。
表VII
硫酸盐浆,3kg疏水物质/吨浆
用喷雾法加疏水物质
疏水物质 实施例 再湿性(g)
参考 33 4.50
E 34 3.81
F 35 3.60
H 36 3.96
K 38 4.26
因此,按本发明方法生产的绒毛比未经处理的绒毛也对血液有更好的液体保留能力。
实施例39
将疏水物质F加于硫酸盐浆(直接加于浆料或喷于浆页)。然后将处理的浆撕碎成绒毛,测定绒毛中存留的疏水物质下的含量。另外再按先有技术做一对比试验,其中是将干的疏水物质F施于干法撕碎的硫酸盐浆(即绒毛)。将此三个绒毛样品进行再湿性试验。结果示于下表VIII中。
表VIII
施加方法 疏水物质F加入量,Kg/t 疏水物质F在绒毛中的存留量,Kg/t 再湿性,g
干疏水物质加于干绒毛(先有技术) 0.6 0.6 4.56
加于浆料 3 0.6 4.44
喷加 1 0.6 4.35
虽然得到的三个绒毛产品含有相同量的疏水物质F,但它们的性质明显不同,很明显按本发明方法生产的绒毛具有明显较好的再湿性特征。

Claims (13)

1.一种生产有改进的吸着能力的绒毛的方法,其中绒毛是用纤维素纤维页撕碎形成的,其特征是纤维页在撕碎前在水存在下用比表面积至少约50m2/g的疏水物质处理纤维。
2.权利要求1的方法,其特征是纤维在处理前的干含量至少约20%。
3.权利要求1或2的方法,其特征在于疏水物质是疏水性低于约0.99wt%残留丁醇的活性炭或沸石,用残留丁醇测试法测定。
4.权利要求1-3任一项的方法,其特征在于纤维是用疏水物质和水组成的混合物喷雾或淋洒的。
5.权利要求1-4任一项的方法,其特征在于纤维在形成浆页前的处理过程中是悬浮在水溶液中的。
6.用任一项前述权利要求的方法制得的绒毛。
7.包括权利要求6的绒毛的吸收制品。
8.用比表面积大于50m2/g的疏水物质处理纤维素纤维以改进由纤维构成的吸收材料的吸着能力的应用。
9.权利要求8的应用,其特征在于疏水物质是疏水性低于0.99wt%残留丁醇的活性炭或沸石,用残留丁醇测试法测定。
10.一种生产吸收材料的方法,该吸收材料由纤维素纤维组成,纤维素纤维是用这种纤维的浆页撕碎得到的,这种材料有改进的吸着能力,其特征在于在撕碎浆页前纤维素纤维已在水的存在下用比表面积至少为50m2/g的疏水物质进行处理。
11.用权利要求10的方法制得的吸收材料。
12.权利要求11的吸收材料,其特征在于该材料是干法形成的非织造物或薄纸。
13.权利要求11的吸收材料,其特征在于该材料是绒毛。
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