CN1238819A - 纸和纸板的制造 - Google Patents

纸和纸板的制造 Download PDF

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CN1238819A
CN1238819A CN97180080A CN97180080A CN1238819A CN 1238819 A CN1238819 A CN 1238819A CN 97180080 A CN97180080 A CN 97180080A CN 97180080 A CN97180080 A CN 97180080A CN 1238819 A CN1238819 A CN 1238819A
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P－O·艾利克森
I·艾利克森
B·哈雅尔玛森
J·G·朗格雷
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Ciba Specialty Chemicals Water Treatments Ltd
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Abstract

纸和纸板是按如下步骤制造的：将阳离子聚合物助留剂加入到纤维素悬浮体中，剪切悬浮体以分解所得的絮凝物，通过在阴离子染料，颜料或光学增白剂存在下加入膨润土或其它阴离子架桥促凝剂的水性组合物来凝结悬浮体，由凝结的悬浮体制成纸。

Description

纸和纸板的制造
本发明涉及用以下方法制备纸或纸板：形成水性纤维素悬浮体，将聚合物助留剂加入到悬浮体中以形成絮凝物，通过剪切悬浮体分解絮凝物以形成微絮凝，通过向悬浮体中加入阴离子架桥促凝剂的水性组合物凝结微絮凝，凝结的悬浮体滤水形成纸片，和干燥纸片。这种普通方法为大家所熟悉。例如Hydrocol(商标)方法涉及这些步骤并且使用膨润土(即阴离子型膨胀土)作为阴离子架桥促凝剂。这种方法在如US4753710,4913775和EP-A-707673中有描述。
一般絮凝悬浮体的形成涉及将一种或多种阳离子聚合物加入到悬浮体中。例如聚合物助留剂经常是一种高分子阳离子聚合物，和/或在方法的早期步骤中可以加入其它阳离子聚合物。例如阳离子淀粉或其它增强剂被加入以增加强度和/或可以加入低分子量阳离子聚合物以提高保留性能和/或其它用途，如控制稠料中的树脂障碍(pitch)。
为了提高干燥纸片的视觉外观，加入会改变纸片视觉外观的阴离子材料是常用的，如颜料或染料或通常加光学增白剂。出于方便和充分混合的原因，这些阴离子材料经常在方法中相对较早的步骤加入，当然是在助留剂之前，甚至经常在稠料步，例如在混料箱中。
因此典型的方法包括和任何所需填充剂一起或在此之前向稠料中加入阴离子光学增白剂，然后加入阳离子淀粉和/或低分子量阳离子促凝剂(它也可以加入稠料中作为树脂障碍控制添加剂)，随后加入阳离子或其它聚合物助留剂和阴离子架桥促凝剂。
这种类型方法已经大规模地使用许多年。
在所有的造纸方法中希望使用最少量的化学添加剂得到最佳性能。因此滚轧工人想使用最少量的聚合物得到最佳的树脂障碍控制，强度，保留性能和滤水性能或其它去水性能，以及使用最少量的光学增白剂，染料或颜料得到最佳视觉外观。
本发明的目的是将用这种方法提供改进的性能。特别是，一个目的是将得到改进的保留性能和去水性能(包括滤水)以使操作员能够使用同样量的化学添加剂而得到提高的去水和保留性能或允许操作员得到相等的去水和保留性能而用更少量的添加剂。另一目的是得到改进的视觉外观，因此允许操作员使用同样剂量的光学增白剂、染料或颜料而得到更好增白或色彩，或使用更少剂量光学增白剂，染料或颜料而得到相同增白或色彩。
根据本发明，造纸和纸板方法包括：
形成水性纤维素悬浮体，
悬浮体中加入聚合物助留剂以形成絮凝，
通过剪切悬浮体分解絮凝以形成微絮凝，
通过向悬浮体中加入包括阴离子架桥促凝剂的水性成分凝结微絮凝，
凝结悬浮体滤水以形成纸片，以及
给纸片染色，
并在这一方法中至少一种阳离子聚合物在剪切之前加入到悬浮体中，以及用于纸或纸板的阴离子光学增白剂和/或染料和/或颜料基本上和阴离子架桥促凝剂的阴离子组合物一起加入到悬浮体中。
因此阴离子光学增白剂，染料或颜料就在阴离子架桥促凝剂的水性组合物之前，之后或一般与它一起加入到剪切的悬浮体中。这些材料可以分开但必须在紧挨的位置添加到悬浮体中或通常在单一的添加位置加入。因此优选阴离子光学增白剂，染料或颜料在它加到悬浮体中之前混入阴离子架桥促凝剂的水性组合物。因此它可以当水性组合物加入到悬浮体中时在线混合或可以预先混合。
本发明适用于任何方法，其中阳离子聚合物在剪切之前加入到悬浮体中，接着加入阴离子架桥促凝剂。实际上这意味着本发明可适用几乎所有的方法，这些方法涉及加入聚合物助留剂，接着加入阴离子架桥促凝剂。这是因为几乎所有这样的方法确实涉及在剪切之前的某一步中加入至少一种阳离子聚合物。
本发明的结果是，我们能够得到去水和保留性能及外观特性的改进的综合性能。
当阳离子聚合物在为得到去水和保留性能的剪切之前加入到悬浮体中时本发明具有特殊的价值，因为本发明随后在去水和保留性能方面得到改进。在本发明的优选方法中，阳离子聚合物作为助留剂被加入。如同在US4388150中提出的，可以使用阳离子淀粉作为助留剂，但是优选一种有足够高分子量以赋予保留性能的合成阳离子聚合物。因此一般它的分子量必须在500,000以上并且通常它具有至少4dl/g的特性粘度。特性粘度是用粘度计的悬浮杠杆在25℃缓冲到pH7.5的水性组合物上测定的。
优选的阳离子助留聚合物大部分是一种或多种烯类不饱和单体的水溶性聚合物。一般它们是丙烯酰胺或其它水溶性烯类不饱和单体与阳离子烯丙基单体如二烷基二甲基氯化铵(DADMAC)或一种阳离子丙烯酸单体如二烷基氨基烷基(甲基)丙烯酸酯或丙烯酰胺作为酸添加剂或优选季铵盐的共聚物。如同在EP202780中描述的，聚合物可以是全部线型的或轻度交联。聚合物可以由于含少量阴离子基团而呈两性的。在本发明使用的适当的高分子量阳离子聚合物类助留剂在如US4753710,4913775和EP-A-308752中有描述。
在使用高分子量阳离子聚合物类助留剂这一普通类型的本发明方法中，用其它阳离子聚合物预处理悬浮体通常是有利的。这可以是阳离子淀粉(在合成阳离子聚合物类助留剂之前)或其它阳离子增强树脂或者可以是一种分子量相对较低但高度荷电并且可以改进保留和去水性能的聚合物。这类适当的聚合物包括聚乙烯亚胺，聚胺，聚(DADMACS)和二氰二酰胺缩聚物。
本发明也包括这样一些方法，其中纤维素悬浮体通过施用这样的聚合物而阳离子化或者用这些的聚合物处理，然后使用非离子或阴离子助留剂。使用阴离子助留剂实现的这种方法在EP-A-308752中有描述，使用非离子或阴离子助留剂的方法在EP-A-707673中有描述。
当在稠料步加入一种阳离子聚合物，一般为高度荷电低分子量阳离子聚合物如上面讨论的聚合物例如以控制树脂障碍时，本发明也是有价值的。适当的低分子量阳离子聚合物在如EP-A-308752和US4913775中有更详细地描述。
在本发明使用的阳离子聚合物剂量可以在常用范围内。因此高分子量助留剂的剂量一般为50～2000，经常为10～1000g/t，以及任何低分子量阳离子聚合物的剂量一般在100～3000，经常在500～2000g/t。在任何方法中聚合物的最佳量是用常用方法的常规试验测定。
虽然在本发明的总量一般在常用范围内，但是在任何特殊方法中赋予特殊保留或去水性能所要求的实际量一般将少于在常用方法中的量，在常用方法中光学增白剂，染料或颜料在早期步骤中被加入。典型地在本发明中阳离子助留剂量比光学增白剂，染料或颜料在早期步骤中加入时的所需量至少少5％并经常至少少10％。在某些情况中可以达少20％～甚至30％。例如典型地该量比在常用方法中的少10～100，经常约20～50g/t。
助留剂和其它前面的聚合物以常用方法在常用的位置加入。它导致絮凝化并且在本发明中如同常用的，通过剪切悬浮体分解絮凝是必要的。只需通过将悬浮体紊流地流经一导管就可以达到足够的剪切，在这种情况下在例如最后的离心滤网后可以加入助留剂。但是一般通过让悬浮体流经一相对较高的剪切混合步骤如一离心过滤网或一扇形泵就可分解。
阴离子架桥促凝剂然后加入到剪切的悬浮体中以凝结微絮凝(一般在最后的高剪切点后面，例如在或接近网前箱处)。这种一般技术经常被认为是超凝结化或微颗粒保留，因为大部分适当的阴离子架桥促凝剂是微颗粒材料。
优选材料是膨润土，也就是说一种膨胀土，它通常基于蒙脱土，锂蒙脱土或高岭土结构。但是使用其它无机阴离子微颗粒或胶态材料也是可能的，如胶态二氧化硅，聚硅酸盐微胶，聚硅酸微胶以及这些物质的铝改性物(参见例如U.S.4643801,EP-A-359552和EP-A-348366)。也可使用阴离子有机微颗粒材料。因此可以使用阴离子有机聚合物乳液。乳化聚合物颗粒由于是由水溶性阴离子单体和一种或多种非溶性单体如丙烯酸乙酯的共聚物而是不溶的，但是优选聚合物乳液是一种水溶性单体材料的交联微乳液。
微颗粒材料的颗粒尺寸一般低于2μm，优选低于1μm以及有时低于0.1μm。例如可以使用尺寸为0.01-0.2μm的阴离子交联聚合物乳液，但是优选架桥促凝剂是膨润土。
架桥促凝剂的量一般至少为300g/t，经常至少1000g/t，例如达3000或甚至5000g/t。
阴离子染料，颜料或光学增白剂可以以任何量加入到悬浮体中，这些量对特殊材料和所希望的效果是常用的。例如商用光学增白剂组合物(例如商标名为Blanchophor P01所售的材料)典型地使用量为500～5000，经常为1000～3000g/t。本发明确实允许减少染料，颜料或光学增白剂的量而同时保持相同的视觉效果，例如典型地减少5～30％。但是一般优选在最后步骤中使用可给出所希望的视觉外观的任何量的光学增白剂、染料或颜料，而不管如果已在早期步骤中加入，则多少量可能是适当的。
纤维素悬浮体可以由任何常用的输入料制得并且可能是干净的或脏的。它可以加填料或不加填料。如果加填料，在悬浮体中的填料量典型地为悬浮体中固体总重量的10～50％。可以使用常用的填料。
以下是一个实施例。
根据US4913775的一般内容进行该方法。填料混入悬浮体，随后分别顺序加入3.5kg/t阳离子淀粉，500g/t聚DADMAC(特性粘度约为1dl/g)，200g/t高分子量阳离子聚合物，在离心过滤网中进行剪切，然后加入1.5kg/t膨润土。阳离子聚合物是丙烯酰胺和二甲基氨基乙基丙烯酸酯季盐的共聚物，其特性粘度为7～10dl/g。
在第一个方法中，在填料之前加入1～3kg/t的光学增白剂。
在第二个方法中，在淀粉之后但在聚DADMAC之前加入大致相同量的光学增白剂。
在第三个方法中，和膨润土一起加入大致相同量的光学增白剂，作为含有膨润土和光学增白剂的水性组合物。
已经发现在第三个方法中的阳离子助留剂量相对于在第一个和第二个方法中使用量可以减少约30g/t(即减至170g/t)而没有损失去水和保留性能。因此根据本发明第三个方法节省15％阳离子助留剂而没有损失去水或保留性能并且保持视觉外观。

Claims (9)

1．纸和纸板的制造方法，它包括：
形成水性纤维素悬浮体，
向悬浮体中加入聚合物类助留剂以形成絮凝，
通过剪切悬浮体分解絮凝物以形成微絮凝，
通过向悬浮体中加入阴离子架桥促凝剂的水性组合物凝结微絮凝，
凝结的悬浮体滤水以形纸片，
干燥纸片，
其中在剪切之前悬浮体中加入阳离子聚合物并且用于纸或纸板的阴离子染料，颜料或光学增白剂基本上和阴离子架桥促凝剂的水性组合物一起加入到悬浮体中。
2．权利要求1的方法，其中聚合物助留剂选自阳离子淀粉和合成的水溶性阳离子聚合物助留剂，其特性粘度至少为4dl/g。
3．权利要求1的方法，其中聚合物助留剂包括由一种或多种烯类不饱和单体形成的水溶性阳离子合成聚合物，聚合物特性粘度至少4dl/g。
4．前面权利要求任何一项的方法，其中阳离子聚合物在聚合物助留剂之前加入到悬浮体。
5．权利要求4的方法，其中在助留剂之前加入的阳离子聚合物选自聚DADMAC，聚亚胺，聚胺和二氰二酰胺聚合物。
6．前面权利要求任何一项的方法，其中阴离子光学增白剂，染料或颜料在加入到悬浮体中之前加入到阴离子架桥促凝剂的水性组合物中。
7．前面权利要求任何一项的方法，其中阴离子架桥促凝剂选自有机和无机微颗粒材料。
8．前面权利要求任何一项的方法，其中阴离子架桥促凝剂包括膨润土。
9．前面权利要求任何一项的方法，其中阴离子光学增白剂和阴离子架桥促凝剂一起被加入。
CN97180080A 1996-11-28 1997-11-27 纸和纸板的制造 Expired - Fee Related CN1098949C (zh)

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