CN103132383A - 在造纸中用于改善纸强度助剂性能的浆料预处理 - Google Patents

在造纸中用于改善纸强度助剂性能的浆料预处理 Download PDF

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CN103132383A
CN103132383A CN2011103820583A CN201110382058A CN103132383A CN 103132383 A CN103132383 A CN 103132383A CN 2011103820583 A CN2011103820583 A CN 2011103820583A CN 201110382058 A CN201110382058 A CN 201110382058A CN 103132383 A CN103132383 A CN 103132383A
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CN103132383B (zh
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赵玉林
李君�
饶庆隆
陈卫国
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ChampionX LLC
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Ondeo Nalco Co
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Priority to PCT/US2012/065856 priority patent/WO2013078133A1/en
Priority to BR112014012671-2A priority patent/BR112014012671B1/pt
Priority to ES12851093.0T priority patent/ES2670673T3/es
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Priority to KR1020147017388A priority patent/KR101971194B1/ko
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Abstract

本发明涉及一种提高由具有大比例的OCC的浆料制得的纸强度的方法、组合物和装置。该方法包括以下步骤：1)提供其内具有大量OCC的纸浆料；2)在向浆料中加入强度剂之前加入强度促进剂；3)向浆料中加入强度剂；以及4)由该浆料制造纸制品。该方法使得廉价的OCC材料可以应用在造纸过程，而不会存在OCC中阴离子垃圾通常引起的质量问题。因此，可以制造出成本低且质量好的纸制品。

Description

在造纸中用于改善纸强度助剂性能的浆料预处理
相关申请的交叉引用
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政府资助的研究或开发的声明
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背景技术
本发明涉及在预处理浆料(furnish)以提高由含有大量阴离子垃圾的浆料制得的纸张最终强度中有用的方法、装置和组合物。纸制品的多种性能，包括强度、浑浊度、平整度、孔隙度、尺寸稳定性、孔径分布、掉毛倾向、密度、刚度、成型性和压缩性由于纸内的纤维素纤维之间存在的结合而变得重要。造纸过程中的机械打浆或匀料(refining)步骤可增强纤维之间的结合能力，在这些步骤中，纤维变得更加柔软且可用表面积增加。
纸制品的强度为具有三类的性能，称为干强度、湿强度或再湿强度和湿纸幅强度。干强度是指干燥的纸张所表现出的强度，通常在测试前以恒定的湿度和室温为条件。湿强度或再湿强度是指纸张在测试前充分干燥再用水再湿润后所表现出的强度。湿纸幅强度是指纤维素纤维垫(mat)在干燥为纸制品之前的强度。强度添加剂为有效地提高这些强度中的一种或几种的组合物。
强度树脂为在造纸工艺的湿法结束，在纸垫或纸张成型之前通常添加的聚合物类，以改善纸制品的强度特性。通常认为强度树脂通过补充内纤维结合的数量而起作用。
干强度添加剂用于提高多种纸制品包括纸、纸板、纸巾的干强度。由于再循环对最终纸具有弱化作用，因此干强度添加剂特别有利于由再循环纤维制造纸制品。另外，干强度添加剂应减少用于实现预定纸浆的预定干强度所需的匀料量，以及匀料所需的相应能耗，而不应该对造纸机械中纤维素网的滤水速率造成不利影响。
美国专利6315866、7556714、2884057和5338406以及美国专利申请12/323976中描述了多种利用聚丙烯酰胺和其他聚合物来增加纸制品强度的方法。然而，当浆料含有大量诸如旧瓦楞纸板(OCC)和机械纸浆等阴离子垃圾时，这些方法都不能达到预期。这认为是由于这类浆料中所含有的极高量的阴离子部分，该阴离子部分阻止强度助剂与纸纤维结合。
因此，提供有利于改善包含大量阴离子垃圾的浆料的强度助剂效果的组合物、方法和装置是非常有利且值得期待的。本节中描述的技术并非构成本文中引用的任何专利、出版物或其他信息为相对于本发明的“现有技术”的陈述，除非具体指定如此。另外，本节不应理解为是指已进行研究或者以37CFR§1.56(a)中定义的无其他相关信息存在。
发明内容
本发明至少有一个实施方式涉及一种提高纸制品强度的方法。所述方法包括以下步骤：a)提供包含纤维的浆料，所述浆料中的所述纤维包含至少10％的含大量阴离子垃圾的纤维；b)在向所述浆料加入强度剂之前加入强度促进剂；c)向所述浆料加入强度剂；以及d)根据造纸方法由所述浆料制造纸制品。
每吨所述浆料中的所述强度促进剂的加入量可为0.01至3lb。所述强度促进剂的RSV介于0.5至15、1至12、2至8和/或3至6之间。含有阴离子垃圾的浆料可为选自由再循环纤维或机械纤维以及它们的任意组合组成的组中的一种。所述强度剂可以是干强度强度剂。所述强度剂可以是淀粉、聚丙烯酰胺、乙醛酸聚丙烯酰胺或它们的任意组合。强度剂可以是干强度强度剂，每吨所述浆料中的干强度强度剂的加入量为0.5至10kg。
本文中说明了其他特征和优点，由以下详细说明中将变得明显。
附图说明
图1是表明本发明提高纸制品的破裂强度的效果图。
图2是表明本发明提高纸制品的耐折性的效果图。
具体实施方式
提供以下定义以确定在本实施方式中如何使用术语，尤其是如何解释权利要求。上述定义的组织仅为了方便，而并非要将任何定义限定为任何特殊种类。
“阴离子垃圾”是指用于造纸工艺中的含OCC浆料的一种性能，表征为存在于浆料中的这种大量的阴离子部分的存在，强度助剂被抑制或阻止与纤维结合，因而损害了最终纸的整体质量。
“干强度添加剂”是指提高最终纸张的干强度的强度添加剂，且包括但不限于美国专利4605702和美国专利申请2005/0161181A1中描述的任何一种强度促进剂组合物，特别是其中描述的多种乙醛酸丙烯酰胺(glyoxylatedacrylamide)/DADMAC共聚物组合物。乙醛酸丙烯酰胺/DADMAC共聚物组合物实例是产品#Nalco64170(由伊利诺伊州内玻维尔市纳尔科公司生产)。
“GPAM”是指乙醛酸聚丙烯酰胺。
“OCC”是指旧瓦楞纸箱(或者旧纸板)。OCC纸浆为之前通过至少两次再循环处理的纸浆，所以其纤维比原始纤维更短更弱。这种较短纤维之间的结合明显更弱，导致了纸强度上非常差的质量，例如破裂强度、耐折强度和抗拉强度。OCC还负载大量的阴离子垃圾，这些阴离子垃圾会导致强度剂的失效。OCC包括但不局限于AOCC(美国旧瓦楞纸箱)，JOCC(日本旧瓦楞纸箱)，EOCC(欧洲旧瓦楞纸箱)和COCC(中国旧瓦楞纸箱)，这些旧瓦楞纸箱具有特定独特的性能和特性在本领域是已知的。
“造纸工艺”是指由纸浆制造纸制品的方法，包括将木屑和/或其他纤维素纤维源磨碎并加入形成纤维素造纸浆料(furnish)水溶液，使该浆料滤水形成纸张，挤压该纸张以去除其它水分，并干燥该纸张。形成造纸浆料、滤水、挤压和干燥的步骤可按照本领域技术人员通常所知的任何常规方式进行。造纸工艺包括纸浆制造。
“强度添加剂”是指在造纸工艺中加入后可提高纸张强度的组合物，该提高可达到10％或更高。
“强度促进剂”是指选自由表氯醇-二甲胺(EPI-DMA)、EPI-DMA氨交联聚合物类、二氯化乙烯和氨的聚合物类、二氯化乙烯聚合物类、二甲胺聚合物类、多官能团二亚乙基三胺缩聚物类、多官能团四亚乙基五胺缩聚物类、多官能团己二胺缩聚物类、多官能团二氯化乙烯缩聚物类、蜜胺聚合物类、甲醛树脂的聚合物类、阳离子带电(charged)乙烯加聚物类、丙烯酰胺与丙烯酸钠的共聚物类、通过水解使一部分丙烯酰胺基团转化为丙烯酸的丙烯酰胺均聚物类、丙烯酰胺和丙烯酸钠的共聚物类、丙烯酰胺和丙烯酸钠与丙烯酸钠的共聚物类以及它们的任意组合组成的组中的组合物。强度促进剂的重均分子量通常在800,000和3,000,000之间，优选在1,000,000和2,000,000之间，最好是在1,200,000和1,500,000Da。低分子量的强度促进剂的重均分子量小于1,200,000Da。中分子量的强度促进剂的重均分子量从1,500,000到2,000,000Da。高分子量的强度促进剂的重均分子量大于2,000,000Da。就RSV来说，强度促进剂的RSV通常介于3和12dl/g之间。
如果本申请中在他处陈述的上述定义或描述与字典中或通过引用合并于本申请的源文件所陈述的常用意思(清楚或模糊)不一致，则本申请特别是权利要求术语应理解为根据本申请中的定义或描述进行解释，而不是根据通常定义、字典定义或通过引用合并的定义来解释。根据以上说明，如果术语仅能通过字典解释来理解，如果该术语由Kirk-Othmer Encyclopedia of ChemicalTechnology，5th Edition，(2005)，(Wiley，John&Sons.Inc.出版)定义，则该定义将控制如何在权利要求中限定该术语。
在本发明至少一个实施方式中，方法包括以下的步骤：1)提供纸张浆料；2)在向该浆料中加入强度剂之前加入强度促进剂；3)向该浆料中加入强度剂；以及4)由该浆料制造纸制品。
不限于解释权利要求中所提供的原理和范围，相对于现有技术的方法，认为加入强度促进剂能够更有效地防止阴离子垃圾和强度剂之间的相互作用。在现有技术的方法中，对浆料加入阳离子材料，如无机凝结剂。这些阳离子材料用于中和阴离子垃圾。认为强度促进剂具有与阴离子垃圾形成结块的最佳的结构和反应性，因此远更有效地阻止阴离子垃圾和强度剂之间的接触。
美国专利12/323,976之前已公开了使用强度促进剂提高强度剂的效果。然而，那是对填料颗粒加入强度促进剂以防止填料颗粒和强度剂之间的相互作用。在本文中，是对浆料而不是填料颗粒加入强度促进剂。在至少一个实施方式中，对聚丙烯酰胺进行乙醛酸处理来制备市场上作为强度剂而周知的GPAM。
在至少一个实施方式中，上述处理的组合物是美国专利6,592,718中说明的组合物的任意一种或组合。具体地，该专利中详细描述的任何一种AcAm/DADMAC共聚物组合物均适用作上述处理的组合物。AcAm/DADMAC共聚物组合物的实例为来自伊利诺伊州内玻维尔市纳尔科公司的产品#N-4690(以下称为4690)。
上述处理的组合物可以是具有适当分子量范围或者RAV值范围的凝结剂。包含在本发明中的凝结剂是公知的，而且可以从市场上购得。
一些适用作上述处理的组合物的凝结剂通过缩聚反应形成。这种类型聚合物的实例包括表氯醇-二甲胺(EPI-DMA)和EPI-DMA氨交联聚合物类。
其它适用作上述处理的组合物的凝结剂包括二氯化乙烯和氨或者加入或者不加入氨的二氯化乙烯和二甲胺的聚合物类、诸如二亚乙基三胺、四亚乙基五胺、己二胺等多官能团胺类与二氯化乙烯的聚合物类以及通过缩合反应制得的聚合物类，如蜜胺、甲醛树脂。
其它适用作上述处理的组合物的凝结剂包括阳离子带电乙烯加聚物，如(甲基)丙烯酰胺、聚合物共聚物三元共聚物，二烯丙基-N，N-双取代卤化铵、甲基丙烯酸二甲基氨基乙酯及其季铵盐、二甲基氨基丙烯酸酯及其季铵盐、甲基丙烯醛基氨基丙基三甲基氯化铵、二烯丙基甲基(β-丙酰胺基)氯化铵、(β-甲基丙烯酰氧基乙基)三甲基铵甲基硫酸酯、季铵化聚乙烯内酰胺、乙烯胺以及用于反应生成曼尼希或者四级曼尼希衍生物的丙烯酰胺或者甲基丙烯酰胺的聚合物、共聚物、三元共聚物。优选地，可使用甲基氯、硫酸二甲酯或者苄基氯生成季铵盐。三元共聚物可以包括阴离子单体，如丙烯酸或者2-丙烯酰胺-2-甲基丙烷磺酸，只要该共聚物的全部电荷为阳离子的即可。这些同时包括乙烯基加成物和缩合物的聚合物的分子量在低至几百到高至几百万的范围内。优选地，这些聚合物的分子量应该在约20,000到约1,000,000的范围内变化。
在至少一个实施方式中，用作处理组合物的凝结剂为丙烯酰胺与丙烯酸钠的共聚物，或者通过水解使一部分丙烯酰胺基团转化为丙烯酸的丙烯酰胺均聚物。在至少一个实施方式中，凝结剂为丙烯酰胺与丙烯酸钠的共聚物。在至少一个实施方式中，凝结剂为丙烯酰胺与丙烯酸钠共聚物，该共聚物具有5-30摩尔％的丙烯酸钠和3～12dL/g的RSV。
可用于本发明的强度剂的代表性实例为GPAM，如纳尔科产品N-64170和N63700。
在至少一个实施方式中，强度促进剂的分子量介于普通的凝结剂的分子量和絮凝剂分子量之间。普通的有机凝结剂(特别是有机凝结剂)通常指具有高电荷密度和较低分子量的聚合物。相比之下，絮凝剂通常指具有低电荷密度和高分子量的聚合物。在至少一个实施方式中，强度促进剂因其中值电荷密度和中值分子量而不同于凝结剂和絮凝剂。在至少一个实施方式中，强度促进剂的浓度或者纤维素与GPAM之间的比值最优为0.1～2kg/t(纤维；GPAM或者强度剂)。纤维的用量通常为0.5到5kg/ton。
实施例
参照以下具体实施方式可更好地理解前述内容，提供实施例旨在说明，而并非要限制本发明的范围。
实施例1
由造纸厂得到稠原料(stock)浆料。该浆料含有40％COCC和60％EOCC，具有3.5％的浆料稠度。将该稠原料用自来水稀释至0.75％的稠度。
在动态滤水仪中以800rpm混合335.0克的0.75％的稀原料来制备手写纸，动态滤水仪具有由固体塑料板覆盖以防止滤水的底筛网。动态滤水仪和混合器由纽约卡梅尔Paper Chemistry Consulting Laboratory.Inc.获得。混合15秒后，加入适量的强度促进剂N-4690(由伊利诺伊州内玻维尔市的纳尔科公司获得，60563)；混合30秒后，加入适量的强度添加剂N-64170(由伊利诺伊州内玻维尔市的纳尔科公司获得，60563)；混合45秒后，加入0.4lb/ton的(活性类)絮凝剂N-61017(由伊利诺伊州内玻维尔市的纳尔科公司获得，60563)。
加入凝聚剂15秒后停止混合，并将该浆料转移至Haage Kothen手写纸模具的定纸框盒(由瑞典AB Lorentzen&Wettre获得)。经过100目成型线滤水形成直径7.9″的手写纸。通过在湿手写纸上放置两张吸墨纸和金属板并用25lb的金属辊辊压6遍而由纸张模具线压出手写纸。移走成型线和一张吸墨纸并在在线侧覆盖一张新吸墨纸。然后将该夹层手写纸放入压力为0.4至0.6MPa的真空下的92至97℃的干燥器中达7分钟。
将成品手写纸在50％相对湿度和23℃的TAPPI标准条件下存放整夜。测定纸张重量(TAPPI测试方法T410om-98)、用来确定填料含量的灰分含量(TAPPI测试方法T211om-93)和抗拉强度(TAPPI测试方法T494om-01)并列于表1。
在表1中，条件1为既没有加入强度促进剂也没有加入干强度添加剂的浆料；条件2为仅具有0.1lb/ton的强度促进剂N-4690的浆料；条件3和4为分别具有3lb/ton和6lb/ton的强度剂N-64170的浆料；条件5和6为分别具有0.1lb/ton的强度促进剂和3lb/ton的强度剂N-64170以及0.1lb/ton的强度促进剂和6lb/ton的强度剂N-64170的浆料。
表1
实施例1和2中的手写纸张性能
Figure BDA0000112566480000081
实施例2
重复实施例1的方法，除了强度促进剂替换为常用的凝结剂，即明矾和聚-DADMAC或N-7607(由伊利诺伊州内玻维尔市的纳尔科公司获得，60563)。同样测定了成品纸性能并列于表1中。在条件7和8中，强度促进剂替换为常用的无机凝结剂明矾；条件9和10中，强度促进剂替换为常用的有机凝结剂聚-DADMAC N-7607。
与条件1相比，仅由强度促进剂处理过的浆料并未增加纸强度(条件2)。将3lb/ton和6lb/ton的强度剂N-64170加入浆料(条件3和4)可将抗拉强度分别提高了18.5％和29％。通过强度促进剂与3lb/ton和6lb/ton的强度促进剂结合处理的浆料(条件5和6)产生更强的强度改善，且抗拉强度分别提高了20.4％和33％。用无机凝结剂明矾(条件7和8)或有机凝结剂N-7607(条件9和10)代替强度促进剂N-4690没有改善N-64170的性能。
尽管本发明可以多种不同方式实施，但本发明具体优选的实施方式为本文中详细说明的实施方式。本公开内容为本发明原理的示例，并非要将本发明限定于所说明的具体实施方式。本文中提及的所有专利、专利申请、科技论文和任何其他参考材料均通过整体引用而合并。而且，本发明包含本文中说明的以及合并于本文中的多种实施方式的一些或所有的任何可能组合。
上述公开内容旨在说明，而非穷尽。本说明书将对本领域普通技术人员暗示了许多变更和替换。所有这些变更和替换都将包含在权利要求的范围内，其中术语“包括”含义为“包括但不限于”。对本领域熟知的人可辨认出本文中说明的具体实施方式的其它等效方案，这些等效方案同样将由权利要求覆盖。
本文中公开的所有范围和参数均应理解为包括任何和所有其内包含的子区间以及端点之间的每一个数值。例如，规定的范围“1至10”应认为包括任何和所有最小值1和最大值10之间(和包含)的子区间；即，所有以最小值为1或更大为开始(例如1至6.1)和以最大值为10或更小为终止(例如2.3至9.4、3至8、4至7)的子区间，以及最终1、2、3、4、5、6、7、8、9和10均包含在此范围内。
这里完成了对本发明优选的和替换的实施方式的说明。本领域技术人员可辨认出本文中说明的具体实施方式的其它等效方案，这些等效方案将由所附权利要求覆盖。

Claims (10)

1.一种提高纸制品强度的方法，所述方法包括以下步骤：
a)提供包含纤维的浆料，所述浆料中的所述纤维包含至少10％的含大量阴离子垃圾的纤维；
b)在向所述浆料中加入强度剂之前加入强度促进剂；
c)向所述浆料中加入强度剂；
d)根据造纸方法由所述浆料制造纸制品。
2.如权利要求1所述的方法，其中每吨所述浆料中的所述强度促进剂的加入量为0.01到3lb。
3.如权利要求1所述的方法，其中所述强度促进剂的RSV介于0.5到15之间。
4.如权利要求3所述的方法，其中所述强度促进剂的RSV介于1到12之间。
5.如权利要求4所述的方法，其中所述强度促进剂的RSV介于2到8之间。
6.如权利要求5所述的方法，其中所述强度促进剂的RSV介于3到6之间。
7.如权利要求1所述的方法，其中所述阴离子垃圾为选自由再循环纤维或机械纤维以及它们的任意组合组成的组中的一种。
8.如权利要求1所述的方法，其中所述强度剂为干强度剂。
9.如权利要求1所述的方法，其中所述强度剂为淀粉、聚丙烯酰胺、乙醛酸聚丙烯酰胺或它们的任意组合。
10.如权利要求8所述的方法，其中所述强度剂为干强度剂，每吨所述浆料中的所述干强度剂的加入量为0.5到10kg。
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US8882964B2 (en) 2014-11-11
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