CN1269855A - 造纸方法 - Google Patents

造纸方法 Download PDF

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CN1269855A
CN1269855A CN98808956A CN98808956A CN1269855A CN 1269855 A CN1269855 A CN 1269855A CN 98808956 A CN98808956 A CN 98808956A CN 98808956 A CN98808956 A CN 98808956A CN 1269855 A CN1269855 A CN 1269855A
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H·约翰斯顿
L·科莱特
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Ciba Specialty Chemicals Water Treatments Ltd
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Abstract

通过与阳离子无机或聚合絮凝剂一起将阴离子淀粉,羧甲基纤维素或其它聚合粘合剂混入纤维素稀浆中,然后借助阴离子溶胀粘土或其它阴离子留着助剂使该悬浮液发生絮凝,而制得纸张。

Description

造纸方法
本发明涉及一种造纸方法(也包括制备纸板)，特别是涉及由淀粉增强的纸张的制备方法。
通过如下方法造纸是标准的做法，所述方法包括：通过添加高分子量的聚合留着助剂而使纤维素悬浮液絮凝；通过成形网使絮凝的悬浮液脱水形成湿纸页；以及对纸页进行干燥。
一种特殊的造纸方法是微颗粒法，其中，利用聚合留着助剂的絮凝作用后接在借助搅拌使絮凝物降解以及借助添加微颗粒材料如膨润土再絮凝。
通过在浓浆阶段或随后阶段的添加，而使低分子量阳离子聚合物包括在悬浮液中是熟知的。另外还熟知的有：就不同的用途包括无机絮凝剂，如聚合氯化铝或明矾。为说明各种方法，特别是以商品名Hydrocol出售的微颗粒法，现参考例如US 4,913,775。
已知可以将阳离子淀粉作为增强助剂添加至造纸过程中的纤维素悬浮液中，并且在一些方法中，还有助于留着率。另外，也已描述一些方法，它包括向纤维素悬浮液中添加未处理过的原淀粉。其中将淀粉添加至纤维素悬浮液中的方法通常具有如下缺点：必须十分小心以便保证淀粉良好的留着率，以致使在通过成形网滤出的白水中没有大量溶解的或未溶解的淀粉。例如参见WO 95/33096。
在GB 2,292,394中描述了一些方法，其中，将能氢键合至纤维素上的阴离子淀粉，羧甲基纤维素或其它聚合粘合剂添加至含有阳离子聚合物的稀浆中，所述阳离子聚合物的分子量大于150,000，优选为一百万或更大，并且所述阳离子聚合物不溶解阴离子粘合剂。另外还能添加阳离子淀粉。
在WO 93/01353中描述了一些方法，其中，将基于淀粉的阴离子留着助剂，纤维素衍生物或不含阳离子基团的瓜耳树胶和铝化合物添加至悬浮液中。其中将阴离子化合物和低分子量阳离子聚合物添加至悬浮液中的这些方法的另一出版物是JP-A-03193996。
尽管可以使各种已知的方法最佳化而在干纸页中得到有用的强度，得到令人满意的短脱水时间和/或纤维和/或粘合剂良好的留着率，但是，仍希望能提供一种方法，该方法能最佳地利用纸页中的粘合剂(并因此有最佳的强度)，以及粘合剂，纤维素悬浮液中纤维和细小纤维良好的留着率，和良好的脱水性能。
通过将高分子量阳离子聚合留着助剂添加至悬浮液中对GB2,292,394中所述的方法进行改进，认为可以实现这些目的，但我们发现，这不能得到任何明显或有用的改进。
根据本发明，造纸(包括纸板)方法包括：
提供纤维素纤维的稀浆悬浮液，
将选自特性粘度不大于3dl/g的水溶性有机聚合絮凝剂和无机絮凝剂的(a)水溶性阴离子或非离子聚合粘合剂和(b)水溶性阳离子物质混入所述悬浮液中，
然后，通过将阴离子留着助剂混入悬浮液中而使其发生絮凝(所述留着助剂可以是微颗粒阴离子留着助剂)，
使絮凝的悬浮液脱水形成一湿纸页，和
对湿纸页进行干燥。
我们惊奇地发现，替代传统的阳离子聚合絮凝剂而添加阴离子留着助剂，在添加粘合剂和阳离子聚合絮凝剂之后，将使悬浮液发生良好的絮凝并随后使脱水速率发生明显的改善和使纤维及细小纤维有良好的留着率。此外，在粘合剂留着率方面不会造成任何明显的损害，并使粘合剂有良好的留着率。
所述纤维素悬浮液可以是由任何常规纤维素原料，包括回用原料形成的任何常规的稀浆。所述稀浆可以是基本上末填充的(即没有有意添加大量的填料)或可以是填充的。
粘合剂是能与纤维素进行氢键合的水溶性物质。即，所述粘合剂能与纸浆中的纤维素纤维粘结，例如粘结剂量至少为1或2％(以干浆计的干粘合剂)，所述粘合剂的留着率常常至少约60或70％，甚至80％。由于如果粘合剂是阳离子的话，粘合剂与纤维素纤维的粘结主要将是由阳离子基团造成的而不是由氢键造成的，因此，实际上粘合剂需要的是非离子或阴离子粘合剂。为了使氢键占主导地位，非离子或阴离子粘合剂通常将是多羟基物质。为了在最终纸页中起粘合剂作用，借此增加纸页的强度，粘合剂必须是聚合的和高分子量的。因此，分子量通常超过5,000，并且经常超过50,000，通常在100,000之上。
实际上，聚合粘合剂通常是纤维素化合物，天然树胶或淀粉，但它也可以是合成聚合物如聚乙烯醇。天然聚合物和改性的天然聚合物包括：纤维素，树胶和淀粉，例如羧甲基纤维素、黄原酸胶、瓜耳树胶、甘露半露聚糖，优选的是阴离子淀粉。该粘合剂优选有可离子化的侧基，所述侧基通常是硫酸盐，羧酸盐或磷酸盐。合适的淀粉包括氧化淀粉，磷酸盐淀粉和羧甲基化淀粉。
粘合剂量通常至少约1％(以干重量悬浮液计的干重量粘合剂)并且至多例如为10％。通常，其用量为1-8％，优选约3％，例如3-5％(即30-50公斤/吨)。
阳离子物质优选为特性粘度(IV)不大于3dl/g的阳离子聚合絮凝剂。在本说明书中，IV为在缓冲至pH 7的1N氯化钠中于25℃，通过气承液柱粘度计测量的特性粘度。优选的是，IV不大于2dl/g，例如为1.5dl/g或更低。通常至少为0.1或0.5dl/g。优选的阳离子聚合絮凝剂具有高电荷密度，例如大于3meq/g，并且通常大于4meq/g。
无机絮凝剂如铝化合物，例如聚合氯化铝可以作为水溶性阳离子物质单独作用，或与聚合絮凝剂组合使用。
优选的阳离子聚合絮凝剂是这样的物质，如聚乙烯亚胺或聚胺(这两种物质优选均是完全季铵化的)、双氰胺缩聚物(通常是基本上完全季铵化的或为盐的形式)和水溶性烯属不饱和单体或单体混合物的聚合物，所述单体混合物由50-100摩尔％阳离子单体和0-50摩尔％其它单体组成。阳离子单体的用量通常至少为80-90摩尔％，并且经常优选均聚物。可以使用的烯属不饱和阳离子单体包括：二烷氨基烷基(甲基)的丙烯酸酯和丙烯酰胺(通常呈季铵形式或其它盐的形式)和二烯丙基二烷基氯化铵，例如二烯丙基二甲基氯化铵(DADMAC)。特别优选的聚合物是DADMAC的均聚物和共聚物。
当聚合物为共聚物时，共聚单体通常是丙烯酰胺，或其它水溶性非离子烯属不饱和单体。
阳离子聚合絮凝剂可以是线性聚合物。另外，它还可以在产生结构的多官能添加剂的存在下来制备，所述添加剂例如包括在聚合物链中的聚烯属不饱和单体如四烯丙基氯化铵、亚甲基二丙烯酰胺以及多官能单体。如果使用的话，这些添加剂的量通常至少为10ppm，一般至少为50ppm。其可以多达200或500ppm。
当添加阴离子留着助剂时，阳离子物质的量通常要超过得到显著留着率所需的量。所述量可足以使悬浮液的ζ-电位约为零或为正值，但即使ζ-电位略微地为负值，通常也能得到令人满意的留着率。实际上，通过形成包含希望量粘合剂的稀浆(考虑到所需的强度性能)，然后在添加各种用量的阳离子物质之后，观察添加留着助剂时的留着作用，可最佳地测定阳离子物质的量。
对于阳离子物质通常不希望的是，包括有任何明显量，或实际上任何量的高分子量阳离子聚合物质(例如特性粘度大于4dl/g)，这是由于使用所述物质在性能方面通常不会产生任何改善，前提条件是，已使用足量无机和/或低分子量的阳离子物质。然而，如果希望的话，可以与上述的阳离子聚合物絮凝剂或无机絮凝剂一起添加其它物质，或在上述的阳离子聚合物絮凝剂或无机絮凝剂之后添加其它物质，前提条件是这些额外的物质不会影响该方法。
阳离子聚合絮凝剂的用量通常为每吨干纤维素悬浮液为0.25-10kg活性聚合物，优选为1-3kg/t。
在该方法中，粘合剂可以在阳离子絮凝剂之前或在阳离子絮凝剂之后添加。粘合剂和絮凝剂可以基本上同时添加。另外，絮凝剂可以一次性添加或分开添加，例如部分在粘合剂之前添加，部分在粘合剂之后添加。在无明显损害结果下，粘合剂和絮凝剂的添加顺序可以方便的形式进行改变。
在用粘合剂和阳离子聚合絮凝剂对悬浮液处理之后，将阴离子留着助剂混入处理过的悬浮液中。所述的混合可以在介质中或在高剪切下进行，但通常是在足够的力下简单地将阴离子留着助剂混入悬浮液中来进行，例如在网前箱处或在网前箱之前进行混合。
以每吨干纤维素悬浮液计，阴离子留着助剂的用量通常为0.5至10公斤，优选为1-4公斤。
阴离子留着助剂是：与末絮凝、处理过的稀浆悬浮液相比，是使处理过的稀浆悬浮液起絮凝并且因此改善滤水性的物质。
所述阴离子留着助剂可以是基本水溶性的阴离子聚合物，因此它可以是例如WO 98/29604中所述的物质。
然而优选的是，所述阴离子留着助剂为：可以是无机或有机的微颗粒阴离子留着助剂。例如，它可以是如在US 5,167,766和US 5,274,055中描述的有机阴离子微颗粒留着助剂。优选的是无机阴离子微颗粒留着助剂。所述物质是熟知的并包括溶胀粘土，通常称为膨润土、胶体二氧化硅、聚硅酸、或聚硅酸微凝胶，以及这些物质的铝改性物。可以使用混合物，例如有机微颗粒和无机微颗粒的混合物。
在用粘合剂和阳离子絮凝剂处理之后和在添加阴离子留着助剂之前，优选的是，没有另外的组分添加至纤维素悬浮液中。
在用阴离子留着助剂处理之后，通过成形网使絮凝的悬浮液脱水形成湿纸页。然后，以标准方法使湿纸页干燥，以便形成干纸页(包括纸板)。
在该方法中，粘合剂在纸页中的留着率优选至少60或70％，更优选至少80％，甚至85或90％或更高。
在本发明中，我们还提供如上所述阴离子留着助剂的使用以改善纤维素悬浮液脱水性能的用途，所述悬浮液已用如上所述种类的粘合剂和阳离子聚合絮凝剂处理过。
在该方法中，我们常常发现，给定体积的回水的脱水时间可降低至在除了不添加阴离子留着助剂的相当的条件下脱水时间的70或60％，甚至可以降低至这些时间的50或40％以下。
实施例
对于每个试验，均使用1升纤维素浆液，浓度为0.5％固体。对于每一种方法，作为粘合剂添加阴离子淀粉，其量为3％，接着加入下表给定剂量的聚合物A。在一些试验中，按以下表给出的剂量添加随后的物质。
聚合物A是IV约1dl/g的聚DADMAC均聚物。
进行脱水试验并测量收集600毫升回水所需的时间。这就是脱水时间。结果列于下表1-3中。表1对一次添加聚合物A进行评估
 淀粉剂量(％)  聚合物A的剂量(kg/t)活性物  脱水时间(秒)
      3333              00.81.63.2       207711
表2高分子量絮凝剂的作用
 淀粉剂量(％)      聚合物A剂量(kg/t)活性物  絮凝剂添加量(g/t)活性物  脱水时间(秒)
    3333         1.61.61.61.6     0低分子阳离子-200中等分子阳离子-200低分子阴离子-200        7896
表3膨润土钠的作用
 淀粉剂量(％)   聚合物A(kg/t)活性物  膨润土剂量(kg/t)活性物   脱水时间(秒)
     333        1.61.61.6          012       723
可以看出，只使用聚合物A时得到了良好的脱水结果，而在随后添加各种高分子量絮凝剂时，观察不到明显的改善。然而，当在聚合物A之后添加膨润土钠时，自由脱水时间将明显改善，该时间将比预期的脱水时间低得多。实施例2
这些试验表明，利用本发明的体系所得到良好的淀粉留着率。在该试验中，使用与实施例1相同的配料。将以干纤维计为3％干淀粉的量的阴离子淀粉添加至该配料中。然后添加阳离子絮凝剂。在某些体系中(本发明的那些体系中)，然后添加另外的组分，即阴离子留着助剂。添加物的剂量和结果列于下表4中。表4
  絮凝剂  絮凝剂剂量(kg/t)  阴离子留着助剂(如果使用的话)  留着助剂剂量(kg/t)  淀粉留着率(％)
 聚合物B      0.60.81.21.62.02.43.6      67909394868584
 聚合物B      1.20.61.2     膨润土钠       2.42.41.2      918191
聚合物B是IV约2dl/g的聚DADMAC的均聚物。

Claims (9)

1.一种造纸方法，包括如下步骤：
提供纤维素纤维的稀浆悬浮液，
将选自特性粘度不大于3dl/g的水溶性有机聚合絮凝剂和无机絮凝剂的(a)水溶性阴离子或非离子聚合粘合剂和(b)水溶性阳离子物质混入所述悬浮液中，
然后，通过将阴离子留着助剂混入悬浮液中而使其发生絮凝，
使絮凝的悬浮液脱水形成一湿纸页，和对湿纸页进行干燥。
2.根据权利要求1的方法，其中阴离子或非离子聚合粘合剂是能与纤维素发生显著氢键合的粘合剂，而阳离子物质是特性粘度不大于3dl/g的阳离子聚合絮凝剂。
3.根据权利要求1或2的方法，其中聚合粘合剂选自：纤维素化合物，天然树胶、淀粉和聚乙烯醇。
4.根据权利要求1或2的方法，其中聚合粘合剂选自：阴离子淀粉和羧甲基纤维素。
5.根据前述任一项权利要求的方法，其中阳离子聚合物选自：聚乙烯亚胺、聚胺、双氰胺聚合物、和水溶性烯属不饱和单体或单体混合物的聚合物，所述单体混合物由50-100摩尔％阳离子单体和0-50摩尔％其它单体组成。
6.根据权利要求5的方法，其中阳离子聚合物是包含水溶性聚烯属不饱和单体的单体聚合物。
7.根据前述任一项权利要求所述的方法，其中，水溶性阳离子物质是80-100％二烯丙基二甲基氯化铵和0-20％丙烯酰胺的聚合物，并且特性粘度低于3dl/g。
8.根据前述任一项权利要求的方法，其中，阴离子留着助剂选自：无机溶胀粘土、胶体二氧化硅、聚硅酸和硅酸盐微凝胶、铝改性的胶体二氧化硅或聚硅酸或聚硅酸盐微凝胶、以及有机微颗粒。
9.根据前述任一项权利要求的方法，其中粘合剂选自：阴离子淀粉和羧甲基纤维素，阳离子物质是特性粘度低于3dl/g的二烯丙基二甲基氯化铵的聚合物，阴离子留着助剂是无机溶胀粘土。
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