CN1243558A - 脱乙酰壳多糖涂布的纸浆和用该纸浆制备的纸以及其制备方法 - Google Patents
脱乙酰壳多糖涂布的纸浆和用该纸浆制备的纸以及其制备方法 Download PDFInfo
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- D—TEXTILES; PAPER
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Abstract
本发明公开了一种涂布过的芳族聚酰胺纤维,其中涂层为少量的脱乙酰壳多糖,该涂布的纤维用于制备改进的强光泽纸。另外本发明还公开了改进的强光泽纸,其中脱乙酰壳多糖以在所有组分上的涂层存在于全部纸张中。
Description
发明背景
发明领域
本发明涉及一种纸浆,由所述纸浆制得的纸张,以及所述纸浆和所述纸张的制备方法。本发明的纸张包括:芳族聚酰胺纸浆,其中含有脱乙酰壳多糖作为添加剂,并且在高温及其它极端条件下能很好地使用所述的纸张。
现有技术说明
1990年1月8日出版的日本特许公开专利申请90-2303披露了脱乙酰壳多糖作为在由天然纤维制得的纸页上的涂层的用途,以便增加其在水中的强度。所述纸页是可生物降解的,并且可用于种植用的农业用途。
EP专利申请123,312(1984年10月31日出版)披露了一种包括有芳族聚酰胺纤维、填料、以及其它材料,且用可固化的热固性树脂浸渍的强光泽纸。存在于纸中的树脂含量从15-60%(重量)。
发明概要
本发明涉及一种脱芳族聚酰胺纤维,该纤维的长度为0.15-10毫米,表面积为0.5-20米2/克,以纤维的重量计,脱乙酰壳多糖涂层量为1-10%(重量)。以纸浆或絮凝物形式的芳族聚酰胺纤维可以是:包含5-95%(重量)芳族聚酰胺纤维,0-20%(重量)粘合剂材料,和10-80%(重量)无机填料的纸张的纤维组分,其中芳族聚酰胺纤维带有脱乙酰壳多糖涂层,以纤维重量计涂层量为1-10%(重量)。
通过将未涂布的纤维分散于脱乙酰壳多糖的水溶液中,并调节溶液的pH值使脱乙酰壳多糖沉积至纤维上,可制得涂布的芳族聚酰胺纤维。另外,还可通过在脱乙酰壳多糖的溶液中对未涂布的絮凝物进行精制得到纸浆于溶液中的分散体;然后调节pH使脱乙酰壳多糖沉积,而制得涂布的纸浆。可通过将脱乙酰壳多糖如此沉积至絮凝物的分散体上而制得涂布的絮凝物。
通过将本发明的脱乙酰壳多糖涂布的芳族聚酰胺纸浆与其它通常在造纸机上芳族聚酰胺纸张的组分混合,可制得纸张;另外还可通过将所有芳族聚酰胺纸张组分混合并在造纸机上添加脱乙酰壳多糖,例如以水溶液的形式,而制得纸张。
详细说明
通常可以发现,当纸张中芳族聚酰胺纤维的含量增加时,纸张的摩擦系数将降低,并且纤维在纸张中的分散将变得不均匀。虽然使用更短的芳族聚酰胺纤维改善了纤维分散体的均匀性,但将使纸张的强度降低,在造纸过程中将产生一些加工问题。使用具有改善纸张强度和增加摩擦系数的更短的芳族聚酰胺纤维是人们所希望的。
本发明的芳族聚酰胺纤维由芳族聚酰胺纤维制得,其中至少85%的酰胺(-CONH-)键直接连接至两个芳香环上。其它的添加剂可与芳族聚酰胺一起使用;并且业已发现,可将多达10%(重量)的其它聚合材料与芳族聚酰胺混合,或者可使用共聚物,该共聚物含有多达10%的取代芳族聚酰胺的二胺的其它二胺或含有多达10%的取代芳族聚酰胺的二酰氯的其它二酰氯。对-芳族聚酰胺是本发明纤维中主要的聚合物,聚(对-亚苯基-对苯二酰胺)(PPD-T)为优选的对-芳族聚酰胺。另外,间-芳族聚酰胺也可用于本发明的纤维中,并且聚(间-亚苯基-间苯二酰胺)(MPD-T)为优选的间-芳族聚酰胺。
本发明的芳族聚酰胺纤维可以是絮凝物或纸浆。芳族聚酰胺絮凝物通过对长的芳族聚酰胺纤维进行切割而制得,如通过US3,063,966;3,133,138;3,767,756;和3,869,430中所述的方法制得的芳族聚酰胺絮凝物。
通过对絮凝物进行精制可制得芳族聚酰胺纸浆,或者如US5,202,184的所述,由配料直接制得芳族聚酰胺纸浆。“纸浆”意指,带有茎且细纤维在其中延伸的芳族聚酰胺材料的颗粒,其中所述的茎通常为圆柱状的且直径约为10-50微米,细纤维为连接至茎上的头发状材料,且直径仅为零点几微米或几微米,长度约10-100微米。在造纸过程中,在制浆时细纤维是相当重要的,它将起钩或系固物的作用,以便将纸张中邻近的颗粒固定在一起,并且提供一完整结构的纸张。
另外,还可使用芳族聚酰胺絮凝物和芳族聚酰胺沉析纤维的混合物制得纸张,其中沉析纤维起将絮凝物和其它纸张组分结合到一起的作用。
对于本发明而言,芳族聚酰胺沉析纤维有时用作粘合剂材料。沉析纤维不是纤维。术语“芳族聚酰胺沉析纤维”指的是,芳族聚酰胺的非粒状的薄膜状颗粒,其中熔点或分解点在320℃以上。所述沉析纤维其平均长度为0.2-1毫米,长宽比从5∶1至10∶1。其厚度尺寸为零点几微米级。在对沉析纤维进行干燥之前,可以湿态使用所述的芳族聚酰胺沉析纤维,并且可以粘合剂的形式沉积,从而物理地缠住纸张的芳族聚酰胺絮凝物组分。可使用US3,018,091中披露的沉析纤维化装置制备本发明纸张中的沉析纤维,其中使聚合物溶液沉淀,并在单一的步骤中进行剪切。
虽然纸浆颗粒的长度是原料絮凝物长度的直接结果,但纸浆和絮凝物的长度通常约为0.15-10毫米。由于表面积是细纤维化程度的量度并且将影响纸张的孔隙率和纤维间连接的有效面积,因此,表面积是用于本发明的纸浆的一个重要特征。在本发明中,所使用的纸浆的表面积为0.5-20米2/克,絮凝物的表面积为0.08-0.6米2/克。由于絮凝物没有纸浆的原纤维化,因此,利用絮凝物制得的纸张在其纸成分间常常还需要有粘合剂,如沉析纤维。
纸浆的加拿大标准游离度(根据TAPPI测试法T 227 om-92测量,该值是纸浆脱水特性的量度)从100毫升至800毫升。另外,将根据TAPPI测试法T 233 cm-82,在Clark分选机的14目筛网上留着的%作为纤维长度的量度。对用于本发明的纸浆而言,该值为0-15%。
脱乙酰壳多糖为通常由壳多糖(聚-β(1,4)-N-乙酰基-D-葡糖胺)的脱乙酰化作用制得的氨基多糖;所述壳多糖是由海洋生物(小虾,螃蟹,龙虾,和鱿鱼等)得到。脱乙酰化作用的程度通常以脱乙酰化的胺基的百分比来表示,并且通常大于50%。脱乙酰壳多糖的分子量是其来源及加工过程的函数。通过在25℃测量在含有0.2M乙酸钠的0.3M的乙酸中的特性粘度值,得到分子量,或者通过在25℃测量于1%乙酸中1%的脱乙酰壳多糖溶液的粘度,得到分子量。用于本发明的脱乙酰壳多糖的粘度从10mPa-sec至22,000mPa-sec,特性粘度从4-20dl/g。脱乙酰壳多糖能以于酸中的溶液使用,所述酸如乙酸,乳酸和柠檬酸;或者能以与所述这些酸的盐的形式使用,如乙酸盐,乳酸盐和柠檬酸盐。
本发明的方法包括利用单独的方法或作为造纸方法的一部分,用脱乙酰壳多糖对芳族聚酰胺纤维进行涂布。当利用单独的方法时,将以乙酸盐,柠檬酸盐,乳酸盐,盐酸盐等形式,在酸性pH,优选在2.5-4.5或稍高的pH值,以芳族聚酰胺纤维计约1-10%(重量)的浓度溶解于水中的脱乙酰壳多糖分散于芳族聚酰胺纤维中。然后通过添加碱将分散体的pH值增加至6.5-11。优选的碱为氯氧化钠,但能使用任何合适的碱。升高pH使得脱乙酰壳多糖沉积至芳族聚酰胺纤维上,因此对芳族聚酰胺纤维进行了涂布。出于种种原因,如果希望的话,可将脱乙酰壳多糖溶解于其中已分散有芳族聚酰胺纤维的水中;在制备涂布的芳族聚酰胺纤维产物时,其添加次序不会造成任何差别。
正如前面所提到的,芳族聚酰胺纸浆是已精制的芳族聚酰胺絮凝物,以便生产细纤维。另外,本发明的方法还可通过如下步骤实施:首先制备芳族聚酰胺絮凝物于脱乙酰壳多糖溶液中的分散体;然后在增加pH值之前,在所述的溶液中将絮凝物精制成纸浆,接着除去水份,并回收脱乙酰壳多糖涂布的芳族聚酰胺纸浆产物。
作为造纸方法的一部分,将包括有以干芳族聚酰胺纤维计为1-10%(重量)浓度的脱乙酰壳多糖涂布的芳族聚酰胺纤维的分散体或造纸配料倾倒在造纸网上,配料中的水份从纤维中除去,然后将所述纤维干燥,得到纸张。以纸张重量计,该纸张通常含有5-95%(重量)的芳族聚酰胺纤维,而芳族聚酰胺纤维通常是已用脱乙酰壳多糖涂布的芳族聚酰胺纸浆。尽管并不是优选的,但可通过将脱乙酰壳多糖添加至包括有芳族聚酰胺纤维的造纸配料中,然后通过将配料的pH值增加至6.5-11使脱乙酰壳多糖沉淀而用脱乙酰壳多糖对纤维进行涂布。在该实施方案中,以纤维的重量计,脱乙酰壳多糖的添加量以沉淀时在芳族聚酰胺纤维上形成1-10%(重量)涂层为准。
业已发现,不管芳族聚酰胺纤维在配料中还是添加至配料中之前用脱乙酰壳多糖进行涂布,将配料的pH增加至6.5-11将能很好地实施本发明。
除此之外,本发明涂布的芳族聚酰胺纤维还在强光泽纸中找到了用途。强光泽纸是:用于电力传输离合器衬片和传输带以便提供更为光滑的衔接,更好的冷却效率以及改善整个传输性能的一种纸张。本发明的强光泽纸通常包括有:以纸浆或絮凝物形式的增强纤维、粘合剂、以及填料。通常用树脂如酚醛树脂或硅氧烷树脂或其混合物对强光泽纸进行浸渍,以便制备离合器衬片。所述强光泽纸通常含有约5-95%(重量)的纸浆或絮凝物,15-85%(重量)的填料和0-10%(重量)的粘合剂,以及0-30%(重量)的其它组分。所述纸浆或絮凝物为本发明的涂布过的芳族聚酰胺纤维。填料可以是无机材料如硅藻土,滑石,碳等。其它组份可包括:其它的纤维如玻璃纤维,或陶瓷纤维等。
本发明的纸张包括1-10%(重量)的脱乙酰壳多糖。当与不含脱乙酰壳多糖的类似的纸张相比时,脱乙酰壳多糖将令人惊奇地增加本发明纸张的摩擦系数值;并且该脱乙酰壳多糖还将明显地增加纸张的强度。正是本发明纤维上及纸张中的脱乙酰壳多糖,赋予了本发明以专利性。
测试方法
摩擦测试步骤
利用Kayness摩擦测试仪(由Kayness,Inc.制造,Morganstown PA19543),对纸页的滑动摩擦系数进行测试。通过添加另外的重量,将通常的测试力从200克增加至1465克,以增加测量的灵敏度。小心地操作,以保证每次测量时不锈钢测试台是清洁的并且试样表面和不锈钢台顶面没被污染。根据Kayness摩擦测试步骤中所推荐的,利用带有“V型”切痕的6.3cm×11.4cm的样板,对测试用试样进行切割。将每个试样包在矩形测试压块的底部并轻拍结实。对于每次测试,该压块均放置在不锈钢台面的相同位置。对于每次测试操作均将量计设置为零,并将测试仪的线速度调节至15.2±0.2厘米/分。对于每次测试,在测试仪停止之前使压块滑动约14厘米,并记录量计上的摩擦力。对于每张纸页而言,除非另有说明,表中是对四个试样进行测试的结果。对于每个试样,读取五个摩擦力读数。摩擦系数为摩擦力和垂直压力的比值。垂直压力等于压块的重量。通过将摩擦力除以1456计算得到了滑动摩擦系数。取如此得到的二十个系数的平均值并计算标准偏差,结果列于表中。在这些测试过程中的实验温度约为23℃。
纸中脱乙酰壳多糖的测量方法
留在纸样上的脱乙酰壳多糖量通过下列步骤进行测量。将一克干燥纸样称重至0.0001克。然后将该试样切成小片并放置于含有250ml 1%乙酸的500ml的烧杯中。对烧杯的内含物进行加热,与此同时在55-60℃搅拌60分钟。然后在冰浴中将烧杯及内含物冷却至低于30℃。然后对烧杯内含物进行过滤,并在真空烘箱的配衡容器中,于130℃将滤液蒸发至干燥,然后通过将残留物放置于强制通风烘箱中于130℃再干燥30分钟。然后将容器和残留物放置于干燥器中进行冷却,然后进行称重。作为空白试验,利用上述步骤对没有试样的250ml的1%乙酸进行操作。按如下计算残留物重量。残留物重量=(容器+残留物)重量-容器重量-1%乙酸空白试验的重量按如下计算脱乙酰壳多糖的百分重量
%脱乙酰壳多糖=(残留物重量/1.37)/试样重量
系数1.37用来计算脱乙酰壳多糖和乙酸脱乙酰壳多糖之间的差,并且该系数为乙酸脱乙酰壳多糖对脱乙酰壳多糖分子量的比值。
实施例1
利用20cm×20cm的实验室手抄纸模具,通过下列步骤制备摩擦试验用的纸张。利用85%(重量)的对-芳族聚酰胺絮凝物(线性密度为2.0dtex,长度约6.4毫米)和15%(重量)的精制间-芳族聚酰胺沉析纤维粘合剂,制备每一种手抄纸。对-芳族聚酰胺絮凝物是聚(对-亚苯基对苯二酰胺)纤维产物,由E.I.du Pont de Nemours and Company出售,商标为KEVLAR49。间-芳族聚酰胺沉析纤维,如US3,756,908所述,根据聚(间-亚苯基间苯二酰胺)制得,并且其Kajaani FS100数均长度为0.49mm,游离度为340ml。此外,将不同数量的脱乙酰壳多糖添加至造纸配料中,从而产生表I和表II中所确定的纸张。利用高分子量的脱乙酰壳多糖生产表I中的纸张,利用低分子量的脱乙酰壳多糖生产表II中的纸张。高分子量脱乙酰壳多糖由DCV Chitin Technologies L.P.以商标VNS-618提供,如以含有1%(重量)乙酸的1%(重量)脱乙酰壳多糖的水溶液的形式提供,并且在25℃时1%溶液的粘度为11,400mPa-sec,特性粘度约为12.5dl/g,而且脱乙酰化度为85.7%。低分子量脱乙酰壳多糖由DCV Chitin Technologies L.P.以商标VNS-589提供,如以含有3%(重量)乙酸的3%(重量)脱乙酰壳多糖的水溶液的形式提供,并且在25℃时1%溶液的粘度为14mPa-sec,而且脱乙酰化度为78.9%。
对于每一纸页而言,将1000ml水倒入不列颠纸浆评估装置(BPEA)中,并且以0.3%含水浆液的形式添加按折干计算为0.4389克上述的聚间亚苯基间苯二酰胺(MPDI)沉析纤维。将按折干计算为2.4871克的聚对亚苯基对苯二酰胺絮凝物(长约6mm,直径约12微米)与适量脱乙酰壳多糖一起添加至该混合物中。再将另外1000ml水添加至BPEA中。对该分散体充分搅拌5分钟。用8000ml水填充手抄纸模具,并将该分散体倒入该模具中。对该模具施加真空,从而除去水份并形成纸页。从模具中取出各纸页,吸干水份,并在190℃进行干燥。然后用平压机于446℃和285KN下对纸页压榨一分钟。然后对每一纸页的定量和厚度进行测量并将这些纸页用于如下所示的摩擦试验。
表I所添加的脱乙 纸中的脱乙酰 定量WT密度 摩擦系数酰壳多糖(%) 壳多糖(%) (g/m2)*(g/cc) 平均值 标准偏差
0 0 67.5 0.305 0.164 0.002
1 0.71 69.2 0.306 0.165 0.002
2 1.38 68.2 0.286 0.167 0.002
4 2.00 69.2 0.301 0.172 0.002
6 3.01 72.9 0.315 0.178 0.002
表II所添加的脱乙 纸中的脱乙酰 定量 WT 密度 摩擦系数酰壳多糖(%) 壳多糖(%) (g/m2) (g/cc) 平均值 标准偏差
0* 0 65.1 0.262 0.165 0.002
1 1.21 66.2 0.260 0.174 0.002
2 1.73 66.8 0.254 0.172 0.002
4 1.73 66.1 0.266 0.173 0.004
6** 2.52 66.8 0.263 0.173 0.003
* 利用该纸张仅读取到十个摩擦读数。
** 利用该纸张仅读取到十五个摩擦读数。
如下实施例2,3和4示出了,用不同数量的脱乙酰壳多糖涂布的纸浆对包含不同数量纸浆的摩擦纸的纸张强度的作用。
对于每一纸页,将PPD-T纸浆和折干计算为0.393克的棉短绒(购自Alpha Cellulose Corporation)添加到约1500ml水中,并在不列颠纸浆评估装置(BPEA)中混合5分钟。PPD-T纸浆的Kajaani FS长度加权的平均长度约0.61mm,算术平均长度约0.18mm,重量加权平均长度约1.48mm。为了建立用于实施本发明的优选的平均长度,使用长度加权的平均长度。通过将所需量的脱乙酰壳多糖(如在1%乙酸中的1%的水溶液)添加到BPEA中的分散于水中的纸浆中,然后中和至pH8.0以上,而制得了脱乙酰壳多糖涂布的纸浆。在此使用的脱乙酰壳多糖与实施例1中使用的高分子量脱乙酰壳多糖(VNS618)相同。以折干计算纸浆的重量%为基础,计算脱乙酰壳多糖的量。以干基纸张的重量百分比计,添加适量的活性炭和硅藻土,并混合5分钟。在该阶段,混合物的pH对于所有纸张来说均在9和10之间。在搅拌的同时将0.098克丁腈胶乳添加到所述混合物中,并添加11克明矾的6%的水溶液,从而使胶乳沉积至造纸配料上。在所有场合,配料的pH值均在5和6之间。以0.44%溶液的形式,添加约10克Bubond 65阳离子留着助剂(购自Buckman Laboratories)。将该配料倒入填充有8000ml水的约20×20cm的手抄纸模具中,对该模具施加真空,从而除去水份并形成纸页。从模具中取出各纸页,用辊吸干并压出水份,并在约120℃进行干燥。然后对每一纸页的定量和厚度进行测量,并利用宽约2.5cm的纸条,在计量长度约5cm的Instron抗张强度测试仪中测量抗张强度。
实施例2
(45%纸浆的纸张)
配料 %干基 干基用量(克)
纸浆 45 4.16
活性炭 35 3.435
硅藻土 15 1.472
棉短绒 4 0.393
丁腈胶乳 1 0.098纸浆中的脱乙 定量 厚度 密度 抗张强度 T.S/酰壳多糖(%) (g/m2) (mm) (kg/cm2) 密度
0 219 0.778 0.282 6.75 23.96
2 235 0.882 0.266 8.72 32.72
4 218 0.778 0.280 11.74 41.94
6 230 0.896 0.257 9.98 38.92
实施例3
(33%纸浆的纸张)
配料 %干基 干基用量(克)
纸浆 33 3.238
活性炭 47 4.612
硅藻土 14 1.472
棉短绒 4 0.392
丁腈胶乳 1 0.098纸浆中的脱乙 定量 厚度 抗张强度酰壳多糖(%) (g/m2) (mm) 密度 (kg/cm2) T.S/密度
0 218 0.746 0.292 4.50 15.39
2 209 0.746 0.279 6.75 24.21
4 219 0.755 0.290 6.82 23.50
6 222 0.819 0.272 6.96 25.60
实施例4
(20%纸浆的纸张)
配料 %干基 干基用量(克)
纸浆 20 1.963
活性炭 60 5.888
硅藻土 15 1.472
棉短绒 4 0.393
丁腈胶乳 1 0.098纸浆中的脱乙 定量 厚度 抗张强度酰壳多糖(%) (g/m2) (mm) 密度 (kg/cm2) T.S/密度
0 210 0.636 0.330 3.52 10.64
2 205 0.645 0.318 3.80 11.93
4 188 0.596 0.316 4.92 15.60
6 202 0.641 0.316 5.41 17.15
实施例5
对于每一纸页,将如前面实施例中所使用的PPD-T纸浆,和0.88克棉短绒添加到约1500ml水中,在韦林氏掺合器中混合5分钟。并转移至BPEA中。通过将所需量的脱乙酰壳多糖(如在1%乙酸中的1%的水溶液)添加到容器中的纸浆分散体中,然后中和至约pH10.0或以上,而制得了脱乙酰壳多糖涂布的纸浆。在此使用的脱乙酰壳多糖与实施例1中使用的高分子量脱乙酰壳多糖(VNS618)相同。以折干计算纸浆的重量%为基础,计算脱乙酰壳多糖的量。以干基纸张的重量计,添加适量的活性炭和硅藻土,并混合5分钟。在搅拌的同时将0.44克丁腈胶乳添加到所述混合物中,并添加25克明矾的5%的水溶液,从而使胶乳沉积至造纸配料上。以25%溶液的形式,添加约25克Bubond 65阳离子留着助剂。将该配料倒入约30×30cm的手抄纸模具中,用约34升水填充该手抄纸模具,并将配料倒入该模具中。对该模具施加真空从而除去水份并形成纸页。从模具中取出各纸页,吸干并压出水份,然后在约120℃进行干燥。然后对每一纸页的定量和厚度进行测量并利用宽约2.5cm的纸条,在计量长度约12.7cm的Instron抗张强度测试仪中测量抗张强度。利用上述步骤进行对比试验,所不同的是没有脱乙酰壳多糖。
配料 %干基 干基用量(克)
纸浆 33 7.28
活性炭 46 10.14
硅藻土 15 3.31
棉短绒 4 0.88
丁腈胶乳 2 0.44纸浆中的脱乙 厚度 抗张强度酰壳多糖(%) (mm) (kg/cm2) T.S/T.S.(0%)
0% 0.761 3.02 1
0.1 0.696 4.08 1.35
0.5 0.759 7.31 2.42
1.0 0.716 7.45 2.47
5.0 0.756 7.52 2.49
实施例6
以类似于实施例5的方式制备这些纸张,所不同的是,在此所使用的纸浆更长,其加拿大标准游离度为629ml,表面积为4.36m2/g,14目的Clark留着率为10.0%。该纸浆的Kajaani FS-200长度加权的平均长度约为1.03mm,算术平均长度约0.20mm,重量加权的平均长度约2.63mm。
(33%纸浆的纸张)纸浆中的脱乙酰 定量 厚度 抗张强度壳多糖(%) (g/m2) (mm) 密度 (kg/cm2) T.S/密度0 201 0.691 0.291 3.52 12.100.1 207 0.728 0.285 5.89 20.680.5 174 0.627 0.277 6.27 22.601.0 193 0.717 0.268 5.23 19.47
实施例7
这些纸张具有如实施例5中的相同组分,利用相同纸浆制得所不同的是,将另外的0.45%胶乳添加到纸张上;并且在两种情况下,将脱乙酰壳多糖直接添加至配料中而不是在将纸浆添加至配料之前涂布至纸浆上。这些结果表明:在造纸过程之前,将脱乙酰壳多糖涂布至纸浆上,以改善强度方面要有效得多。脱乙 定量 厚度 抗张强度酰壳多糖(%) (g/m2) (mm) 密度 (kg/cm2) T.S/密度
0 206 0.648 0.318 5.76 18.14添加至配料中纸浆的2% 229 0.841 0.272 4.88 17.93添加至配料中纸浆的3% 226 0.742 0.304 8.43 27.63
纸浆(湿)的1.5% 225 0.845 0.265 6.76 25.45
实施例8
类似于实施例5制备这些纸张,所不同的是含有如下不同的组分。另外,通过在1%乙酸中1%溶液的粘度确定的脱乙酰壳多糖的分子量也不同。以乳酸盐形式从DCV Chitin Technologies L.P.得到了5700cps的脱乙酰壳多糖,商品名为RNS-049,特性粘度为9.5dl/g。
配料 %干基 干基用量(克)
纸浆 33 3.238
活性炭 47 4.612
硅藻土 15 1.472
棉短绒 4 0.392
丁腈胶乳 1 0.098脱乙 定量 厚度 抗张强度酰壳多糖(%) (g/m2) (mm) 密度 (kg/cm2) T.S/密度没有 222 0.752 0.297 4.29 14.4411,400cps(85.7%DEA)V 244 0.838 0.296 6.89 23.28NS-6185700cps(83.2%DEA)RNS 240 0.863 0.277 6.05 21.83-0495700cps(83.2%DEA)RNS 244 0.813 0.303 6.47 21.35-049
实施例9
本实施例证明:利用已涂布有本发明的脱乙酰壳多糖的纤维,而不是仅仅混有脱乙酰壳多糖的纤维的益处。在本实施例中,将7.28克PPD-T纸浆分散于1500ml水中,并以在1%乙酸中的1%水溶液形式将所需量的脱乙酰壳多糖添加其中。在下面所示的场合,将纸浆分散体中和至pH约8,从而使脱乙酰壳多糖沉淀,然后从分散体中蒸发出水份,从而得到干的脱乙酰壳多糖涂布的纸浆。
在下面的另一种情况下,从纸浆分散体中蒸发出水份,然后不中和脱乙酰壳多糖,以便得到纸浆和脱乙酰壳多糖的干混合物。
利用这些纸浆和脱乙酰壳多糖组份,通过实施例5的步骤制备纸张,结果列于下表中:纸浆中的脱乙 厚度 抗张强度酰壳多糖(%) (mm) 密度 (kg/cm2) T.S/密度2%中和至pH8然后干燥 0.927 0.351 7.49 21.351%干燥的 0.953 0.335 5.80 17.312%干燥的 0.940 0.356 5.38 15.113%干燥的 0.978 0.347 5.86 16.90
Claims (14)
1.一种芳族聚酰胺纤维,其长度为0.15-10毫米,表面积为0.5-20平方米/克,以纸浆重量计的脱乙酰壳多糖的涂层量为1-10%。
2.权利要求1的纤维,其中在1%乙酸中的1%脱乙酰壳多糖的溶液粘度为10-22,000毫帕-秒。
3.权利要求1的纤维,其中纤维为芳族聚酰胺絮凝物。
4.权利要求1的纤维,其中纤维为芳族聚酰胺纸浆。
5.一种强光泽纸,包含5-95%(重量)的芳族聚酰胺纤维,和10-80%(重量)无机填料,其中芳族聚酰胺纤维带有脱乙酰壳多糖涂层,以纤维重量计的涂层量为1-10%(重量)。
6.权利要求5的强光泽纸,其中该纸的摩擦系数与相似的不含脱乙酰壳多糖的纸相比至少大5%。
7.一种制备涂布有脱乙酰壳多糖的芳族聚酰胺纸浆的方法,包含如下步骤:
(a)将芳族聚酰胺纤维分散于脱乙酰壳多糖的水溶液中,该溶液的pH值为2.5-4.5,以芳族聚酰胺纤维计浓度为1-10%(重量),从而得到芳族聚酰胺纤维的分散体;
(b)将所述分散体的pH值改变成6.5-11,使脱乙酰壳多糖沉淀,并涂布分散的芳族聚酰胺纤维;和
(c)从水中分离出以脱乙酰壳多糖涂布的纤维。
8.权利要求7的方法,其中芳族聚酰胺纤维为芳族聚酰胺纸浆。
9.权利要求7的方法,其中,使脱乙酰壳多糖溶解以制备脱乙酰壳多糖溶液,然后将芳族聚酰胺纤维分散于所述溶液中。
10.权利要求7的方法,其中,使芳族聚酰胺纤维分散,以制备芳族聚酰胺纤维的分散体,然后将脱乙酰壳多糖溶解于所述的分散体中。
11.权利要求7的方法,其中,芳族聚酰胺纤维为芳族聚酰胺絮凝物,并且其中在步骤(a)之后和步骤(b)之前,对芳族聚酰胺絮凝物进行精制,以制备芳族聚酰胺纸浆。
12.一种制备包含芳族聚酰胺纸浆的纸张的方法,包含如下步骤:
(a)形成含水纸张配料,所述配料包括:以纸张总重量计为5-95%的芳族聚酰胺纤维,其中该纤维的长度为0.15-10毫米,以该纤维的重量计,脱乙酰壳多糖涂层的重量为1-10%(重量);
(b)将步骤(a)得到的配料倾倒在造纸网上,从而从芳族聚酰胺纤维中除去水份;和
(c)对芳族聚酰胺纤维进行干燥,从而得到一纸张。
13.权利要求12的方法,其中,通过如下步骤制得步骤(a)的配料:
(i)将芳族聚酰胺纤维分散于脱乙酰壳多糖的水溶液中,所述溶液的pH值为2.5-4.5,以芳族聚酰胺纤维的重量计的浓度为1-10%(重量);
(ii)将所述水溶液的pH值变成6.5-11。
14.权利要求12的方法,其中,在步骤(a)之后且在步骤(b)之前,将配料的pH变成6.5-11。
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US08/781,331 US5827610A (en) | 1997-01-10 | 1997-01-10 | Chitosan-coated pulp, a paper using the pulp, and a process for making them |
US08/781,331 | 1997-01-10 |
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US (3) | US5827610A (zh) |
EP (1) | EP0953081B1 (zh) |
JP (1) | JP4338224B2 (zh) |
KR (1) | KR100480851B1 (zh) |
CN (1) | CN1119456C (zh) |
AU (1) | AU726105B2 (zh) |
BR (1) | BR9806730A (zh) |
CA (1) | CA2275199C (zh) |
DE (1) | DE69804586T2 (zh) |
EA (1) | EA001139B1 (zh) |
ES (1) | ES2172871T3 (zh) |
TW (1) | TW413705B (zh) |
UA (1) | UA47504C2 (zh) |
WO (1) | WO1998030752A1 (zh) |
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CN1293155C (zh) * | 2002-04-02 | 2007-01-03 | 阿尔斯特罗姆公司 | 涂有基于脱乙酰壳多糖的涂层的载体及其制造方法 |
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AU5908898A (en) | 1998-08-03 |
TW413705B (en) | 2000-12-01 |
KR20000070014A (ko) | 2000-11-25 |
CA2275199C (en) | 2005-08-23 |
EA001139B1 (ru) | 2000-10-30 |
WO1998030752A1 (en) | 1998-07-16 |
US5998026A (en) | 1999-12-07 |
BR9806730A (pt) | 2000-02-29 |
ES2172871T3 (es) | 2002-10-01 |
JP4338224B2 (ja) | 2009-10-07 |
US5827610A (en) | 1998-10-27 |
AU726105B2 (en) | 2000-11-02 |
KR100480851B1 (ko) | 2005-04-07 |
UA47504C2 (uk) | 2002-07-15 |
CN1119456C (zh) | 2003-08-27 |
EP0953081A1 (en) | 1999-11-03 |
DE69804586D1 (de) | 2002-05-08 |
EA199900634A1 (ru) | 2000-02-28 |
DE69804586T2 (de) | 2002-11-14 |
EP0953081B1 (en) | 2002-04-03 |
US6139688A (en) | 2000-10-31 |
CA2275199A1 (en) | 1998-07-16 |
JP2001508506A (ja) | 2001-06-26 |
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