CN1224474A - 生产增强纤维组合物的方法 - Google Patents
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Abstract
本发明涉及一种生产增强纤维组合物的方法,该组合物含有以Ⅱ型纤维素的晶体结构存在的纤维素纤维,该方法使纤维组合物与N-甲基吗啉-N-氧化物(NMMO)水溶液在高温下接触,并随后清洗纤维组合物,其特征在于,接触过程按如下关系式进行:-947+0.30xlog(10)t+0.046xT-3.53xC+645xlog(10)C其中t表示以分钟计的纤维组合物与NMMO水溶液接触的时间,T表示NMMO水溶液的温度,以℃计,而C是以%表示的NMMO水溶液中NMMO的质量浓度,在温度T小于130℃且质量浓度C介于70%和84%之间的条件下,关系式的值应控制在0.30—1.70之间。
Description
本发明涉及一种生产增强纤维组合物的方法,该组合物含有以Ⅱ型纤维素的晶体结构存在的纤维素纤维,所述方法包括使纤维组合物与N一甲基吗啉-N-氧化物(NMMO)水溶液在高温下接触,并随后清洗纤维组合物。
在本说明及所附的权利要求中,“纤维组合物”一词是指任何种类的织物,非织造织物或无定向纤维网。
在过去的几年里,有多种将纤维素溶于有机溶剂、有机溶剂与无机盐形成的混合物或溶于盐溶液而不形成衍生物的方法被作为粘胶纤维化的可选方法。BISFA(国际人造丝及合成纤维标准化局)将由这些溶液制得的纤维素纤维通称为可溶纤维(lyocell).根据BISFA定义,可溶纤维(lyocell)是一种通过纺丝过程从有机溶剂中得到的纤维素纤维。“有机溶剂”,BISFA将其理解为一种有机化学制剂和水的混合物。
而到目前为止,只有一种生产可溶纤维(lyocell)型纤维素纤维的方法在大规模生产中被接受,即氧化胺方法。在该方法中,优选N-甲基吗啉-N-氧化物作为溶剂(NMMO)。在接下来的说明中,缩写“NMMO”代指“氧化叔胺”,此外NMMO还代表目前优选的N-甲基吗啉-N-氧化物。
氧化叔胺曾长期已知作为纤维素的可选溶剂。比如从美国No.2,179,181专利可以知道,氧化叔胺可以溶解高质量的化学纸浆而不形成衍生物,且纤维素的成型物如纤维可以通过析出作用从此溶液中得到。美国专利Nos.3,447,939,3,447,956和3,508,941进一步介绍了以氧化环胺作为优选溶剂生产纤维素溶液的方法。在所有这些方法中,纤维素均在高温下被物理溶解。
在申请人的EP-A-0356419介绍的方法中,优选使用一种薄层处理设备,其中碎纸浆溶于叔胺氧化物水溶液形成的悬浊液铺散成薄层,在热表面上传送,同时薄层表面暴露于真空中。在热表面上传送悬浊液的过程中,水被蒸发而纤维素被溶解,从而可纺的纤维素溶液从薄层处理设备排放出来。
已经知道一种对纤维素溶液进行纺丝的方法和设备,比如,申请人的WO93/19230。在该方法中,对热的纺丝溶液进行纺丝,而后将所得细丝引入凝固浴以使其中所含的纤维素析出,细丝在被引入析出浴缸前进行了冷却。冷却是在成型后马上进行的,且优选在成型纤维素的水平方向吹风。
德国专利No.902427介绍了通过含5-15%NaOH的碱浴,使纤维素纤维织物得到增强的过程。碱浴使纤维素纤维膨胀从而得到增强。
申请人的WO95/07386介绍了一种造纸的方法,该方法中粉碎纤维素物质的悬浊水溶液经机械处理后,进入成纸过程,该悬浊液含有叔胺氧化物。此方法可用于高强度纸张的生产。
US-A-3,447,956介绍了一种对纤维物质进行增强的方法。在增强过程中,纤维物质浸渍于一种胺氧化物并加热到一定温度,在该温度下胺氧化物能够对纤维物质进行增强。建议使用的纤维物质包括含有天然纤维素纤维,如木纸浆,棉花,亚麻,以及合成纤维,如人造纤维(粘胶纤维)的织物和非织造织物。特别优选用胺氧化物处理纸张。在此过程中,NMMO显然是作为熔融态或液态的一水合物或被溶解于一种可蒸发的挥发性溶剂中使用的。
WO96/37653介绍了具有纤维素涂层,经浸渍或表层覆盖的纤维组合物。这些纤维组合物的生产是通过在纤维组合物的一侧涂敷纤维素的NMMO水溶液,而后在水浴中凝固表层来进行的。
US-A-4,196,282介绍了NMMO/H2O/纤维素形成的三成分系统和所谓的“溶解框架”,即纤维素溶解于NMMO水溶液的条件。
此外,还知道纤维素纤维可以用NMMO溶胀(Chancyetal.,“纤维素在胺氧化物/水系统中的溶胀溶解”;J.App.Pol.Sci:Appl.Pol.Symp.37,239-259(1983)).
本发明的目的是提供一种最初定义的那类方法,该方法中纤维组合物的增强过程不需繁琐地对挥发性溶剂进行蒸发,而且不需使用NMMO的一水合物或通过蒸发制备NMMO的一水合物。
根据本发明,该方法生产的增强纤维组合物含有的纤维素纤维中的纤维素是以Ⅱ型纤维素的晶体结构存在的,该方法包括使纤维组合物与N-甲基吗啉-N-氧化物(NMMO)水溶液在高温下接触,并随后清洗纤维组合物,其特征在于,接触过程按如下关系式进行:
-947+0,30xlog(10)t+0,046xT-3,53xC+645xlog(10)C其中t表示以分钟计的纤维组合物与NMMO水溶液接触的时间,T表示NMMO水溶液的温度,以℃计,而C是以%表示的NMMO水溶液中NMMO的质量浓度,在温度T小于130℃且质量浓度C介于70%和84%之间的条件下,关系式的值应控制在0.30-1.70之间,且优选0.5-1.5之间,而且,特别优选0.8-1.2之间的值。
本发明是基于如下的发现,为了增强纤维素纤维组合物,如非织造织物,所提到的三个参数,即NMMO溶液的浓度,温度和浸渍时间,显然是必要和充分的,而且它们的选择必须满足上面的关系式。如果相反,所选参数使得关系式的值小于0.30,组合物则不会得到增强。而另一方面,如果所选参数使得关系式的值大于1.70,则发现纤维组合物在NMMO溶液中被溶解。
根据本发明,该方法的温度T优选小于100℃。
根据本发明,该方法的具体实施方案的的特征在于,清洗前纤维组合物经过了压制。压制可以通过简单的方式进行,如,通过将非织造织物引入二个滚筒间,并在纤维组合物上施加一定压力来实现。当使用的纤维组合物中含有至少部分经过胺氧化物方法或粘胶纤维方法生产的纤维时,本发明中的方法证明是特别成功的。
本发明将通过下面的实施例得到更详细的解释。
一般工作指导
将轻轻打过针眼的粘胶纤维非织造织物置于二个筛板之间浸入NMMO水溶液进行浸渍,每块非织造织物的大小均为12×16cm而单位面积重量约为70g/cm2,随后用实验室压制机(压制压力:3巴;相当于在12cm宽的非织造织物上线压强为12.6N/mm)压制浸渍过的非织造织物。此后,压制过的非织造织物用自来水清洗15分钟。
实施例
根据以上的工作指导,进行数次测试,且按本发明的要求控制参数,即各次测试的NMMO溶液的浓度(质量百分比%,根据溶液的总质量),温度(℃)和浸渍时间(分钟)的取值见下面的表1。所有实施例均遵从上面定义的关系式。各参数下的关系式值显示于表中。
表1实施例 NMMO- 浓度 温度 时间 值1 84,0 80 0,08 0,952 82,0 80 0,08 1,303 82,0 70 0,17 0,944 80,6 70 0,50 1,205 80,6 80 0,08 1,426 80,6 80 0,50 1,667 78,2 70 1,00 1,298 76,2 70 0,50 1,009 76,2 80 0,17 1,3210 73,9 70 4,00 0,8111 74,2 80 0,50 1,0712 74,2 90 0,17 1,3913 71,9 90 2,00 1,0214 71,9 100 0,17 1,1615 70,0 100 0,50 0,49
实施例1至15属于本发明的范围,因为由这些NMMO浓度,温度和浸渍时间得到的关系式值均在本发明定义的范围内。结果发现所有按照本发明处理的非织造织物均得到了增强。
对于包含通过胺氧化物方法生产的纤维的非织造织物,同样取得了良好的效果。
比较例
为了比较,按照一般工作指导进行了额外测试,但所选参数不满足关系式的要求。这些实施例归纳于表2。
表2实施例 NMMO- 浓度 温度 时间 值16 82,0 90 0,17 1,8617 80,6 80 1,00 1,7518 80,6 90 0,08 1,8819 78,2 80 2,00 1,8420 78,2 90 0,08 1,8821 76,2 90 0,50 1,9222 76,2 100 0,08 2,1423 74,2 100 0,08 1,7524 72,2 70 4,00 0,2925 72,2 120 4,00 2,5926 70,0 80 12,0 -0,1027 70,0 90 2,00 0,2128 70,0 100 0,08 0,25
在实施例16至23和25中,所选参数使得关系式的值大于1.70,非织造织物在NMMO溶液中溶解。
在实施例24和26至28中,所选参数使得关系式的值小于0.30,非织造织物不能得到增强。
Claims (7)
1.一种生产增强纤维组合物的方法,该组合物含有纤维素纤维,其中的纤维素是以Ⅱ型纤维素的晶体结构存在的,该方法使纤维组合物与N-甲基吗啉-N-氧化物(NMMO)水溶液在高温下接触,并随后清洗纤维组合物,其特征在于,接触过程按如下关系式进行:-947+0,30xlog(10)t+0,046xT-3,53xC+645xlog(10)C其中t表示以分钟计的纤维组合物与NMMO水溶液接触的时间,T表示NMMO水溶液的温度,以℃计,而C是以%表示的NMMO水溶液中NMMO的质量浓度,在温度T小于130℃且质量浓度C介于70%和84%之间的条件下,关系式的值应控制在0.30-170之间。
2.根据权利要求1所述的方法,其特征在于,所选参数t,T和C使得关系式的值介于0.5-1.5之间。
3.根据权利要求2所述的方法,其特征在于,所选参数t,T和C使得关系式的值介于0.8-1.2之间。
4.根据权利要求1-3中任一项所述的方法,其特征在于,温度T小于100℃。
5.根据权利要求1至4中任何一项所述的方法,其特征在于,纤维组合物在清洗前被压制。
6.根据权利要求1至5中任一项所述的方法,其特征在于,用来进行增强的纤维组合物中的纤维至少部分是通过胺氧化物方法生产的。
7.根据权利要求1至5中任一项所述的方法,其特征在于,用来进行增强的纤维组合物中的纤维至少部分是通过粘胶法生产的。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA319/97 | 1997-02-25 | ||
AT0031997A AT404368B (de) | 1997-02-25 | 1997-02-25 | Verfahren zur herstellung eines verfestigten faserverbundes |
ATA319/1997 | 1997-02-25 | ||
PCT/AT1998/000040 WO1998038373A1 (de) | 1997-02-25 | 1998-02-25 | Verfahren zur herstellung eines verfestigten faserverbundes |
Publications (2)
Publication Number | Publication Date |
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CN1224474A true CN1224474A (zh) | 1999-07-28 |
CN1105798C CN1105798C (zh) | 2003-04-16 |
Family
ID=3487424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN98800507A Expired - Lifetime CN1105798C (zh) | 1997-02-25 | 1998-02-25 | 生产增强纤维组合物的方法 |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0901533B1 (zh) |
JP (1) | JP2000509771A (zh) |
CN (1) | CN1105798C (zh) |
AT (2) | AT404368B (zh) |
AU (1) | AU727252B2 (zh) |
BR (1) | BR9805914A (zh) |
CA (1) | CA2251728A1 (zh) |
DE (1) | DE59800265D1 (zh) |
ES (1) | ES2152745T3 (zh) |
ID (1) | ID20258A (zh) |
NO (1) | NO310205B1 (zh) |
WO (1) | WO1998038373A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105728565A (zh) * | 2016-04-22 | 2016-07-06 | 安徽联盟模具工业股份有限公司 | 转动翻板式无压痕模具 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009028306B4 (de) * | 2009-08-06 | 2011-04-21 | Tpr Fiberdur Gmbh & Co. Kg | Doppelrohr |
PL2363108T3 (pl) | 2010-03-02 | 2018-04-30 | Neubourg Skin Care Gmbh & Co. Kg | Formulacje piankowe zawierające co najmniej jeden triterpenoid |
DE202015102564U1 (de) | 2015-05-19 | 2015-08-13 | W. Pelz Gmbh & Co. Kg | Oraltabakpackung |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE902427C (de) * | 1948-10-12 | 1955-04-04 | Dr Otto Eisenhut | Verfahren zur Herstellung fester, waschbarer, gewebeaehnlicher, verfilzter Stoffe aus Cellulosefasern ohne Spinnen und Weben |
US3447956A (en) * | 1966-09-02 | 1969-06-03 | Eastman Kodak Co | Process for strengthening swellable fibrous material with an amine oxide and the resulting material |
AT401072B (de) * | 1993-09-06 | 1996-06-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von papier |
JP3488302B2 (ja) * | 1995-01-31 | 2004-01-19 | ユニチカ株式会社 | セルロース繊維布帛の風合加工方法 |
JP3445865B2 (ja) * | 1995-04-06 | 2003-09-08 | 花王株式会社 | セルロース系繊維改質法 |
EP0827557A1 (de) * | 1995-05-22 | 1998-03-11 | Akzo Nobel N.V. | Mit einer cellulosischen beschichtung, imprägnierung oder umhüllung versehene formkörper |
-
1997
- 1997-02-25 AT AT0031997A patent/AT404368B/de not_active IP Right Cessation
-
1998
- 1998-02-25 AT AT98903942T patent/ATE196329T1/de not_active IP Right Cessation
- 1998-02-25 CN CN98800507A patent/CN1105798C/zh not_active Expired - Lifetime
- 1998-02-25 AU AU62001/98A patent/AU727252B2/en not_active Ceased
- 1998-02-25 DE DE59800265T patent/DE59800265D1/de not_active Expired - Lifetime
- 1998-02-25 JP JP10537058A patent/JP2000509771A/ja active Pending
- 1998-02-25 ID IDW980103A patent/ID20258A/id unknown
- 1998-02-25 ES ES98903942T patent/ES2152745T3/es not_active Expired - Lifetime
- 1998-02-25 CA CA002251728A patent/CA2251728A1/en not_active Abandoned
- 1998-02-25 BR BR9805914A patent/BR9805914A/pt active Search and Examination
- 1998-02-25 WO PCT/AT1998/000040 patent/WO1998038373A1/de active IP Right Grant
- 1998-02-25 EP EP98903942A patent/EP0901533B1/de not_active Expired - Lifetime
- 1998-10-20 NO NO19984883A patent/NO310205B1/no not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105728565A (zh) * | 2016-04-22 | 2016-07-06 | 安徽联盟模具工业股份有限公司 | 转动翻板式无压痕模具 |
Also Published As
Publication number | Publication date |
---|---|
JP2000509771A (ja) | 2000-08-02 |
ES2152745T3 (es) | 2001-02-01 |
NO984883L (no) | 1998-10-20 |
EP0901533A1 (de) | 1999-03-17 |
WO1998038373A1 (de) | 1998-09-03 |
AU6200198A (en) | 1998-09-18 |
NO310205B1 (no) | 2001-06-05 |
DE59800265D1 (de) | 2000-10-19 |
CN1105798C (zh) | 2003-04-16 |
AT404368B (de) | 1998-11-25 |
BR9805914A (pt) | 1999-08-24 |
ATE196329T1 (de) | 2000-09-15 |
EP0901533B1 (de) | 2000-09-13 |
AU727252B2 (en) | 2000-12-07 |
CA2251728A1 (en) | 1998-09-03 |
ID20258A (id) | 1998-11-12 |
ATA31997A (de) | 1998-03-15 |
NO984883D0 (no) | 1998-10-20 |
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