CN101529021A - 提高纸强度的方法 - Google Patents
提高纸强度的方法 Download PDFInfo
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- CN101529021A CN101529021A CNA2007800394815A CN200780039481A CN101529021A CN 101529021 A CN101529021 A CN 101529021A CN A2007800394815 A CNA2007800394815 A CN A2007800394815A CN 200780039481 A CN200780039481 A CN 200780039481A CN 101529021 A CN101529021 A CN 101529021A
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
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- D21H21/18—Reinforcing agents
Abstract
本发明提供了制备强度提高了的纸或纸板的方法，该方法包括步骤：i)提供纤维素的稠浆料，ii)将步骤i)的稠浆料稀释形成稀浆料，iii)将步骤ii)的稀浆料在金属丝上排水形成网，及iv)将步骤iii)的网干燥形成纸或纸板，其中步骤(i)的纤维素稠浆料包含有机聚合物微粒，以及可由上述方法获得的纸。
Description
本发明涉及制备强度提高的纸或纸板的方法并涉及可通过该方法获得的纸或纸板。
当今用于制备纸的机器由湿端部分、压榨部分、干燥器部分和计时部分组成。在湿端部分中，约3％纤维/水的稠浆料用水或循环水(白水)稀释，通常在风扇式泵的进口处，形成约1％纤维的稀浆料，该浆料通过压头箱装载到一条或多条金属丝上，在其中形成网，并收集排出的水(白水)。在湿端部分的各加入点可将各种化学品加入到纤维中，以改善最终纸的性质或纸制备的方法。
例如，干强度剂例如淀粉可加入到湿端部分中，以改善最终纸的强度。通常将阳离子淀粉加入到稠浆料中和/或将天然淀粉喷到形成的网上。在湿端部分中加入淀粉的一个缺点是，所收集的白水含有淀粉。白水中淀粉的存在可导致细菌的过量生长和粘液的形成，而白水必须要么作为昂贵的废弃物弃去要么在可能循环前用大量生物杀灭剂处理。通过喷在形成的网上施加淀粉的另一个缺点是，由于用于喷淀粉的喷嘴容易堵塞，机器经常出现运转能力问题。
湿网强度涉及造纸过程期间湿纸的强度。湿网的强度越强，将纸从金属丝导入压榨部分进而从压榨部分导入干燥器部分就越容易。因此，湿网强度的增加导致造纸机器的运转能力更好。湿网强度对各部分之间不具有足够的引导的造纸机器，例如具有开式牵引的机器尤其重要。
本发明的目的是提供用于制备强度提高的，特别是内部粘合强度以及湿网强度提高的纸或纸板的方法。另外，该方法将显示良好的保持和形成。
权利要求1的方法和权利要求7的纸
用于制备纸或纸板的本发明方法包括步骤：
i)提供纤维素的稠浆料，
ii)将步骤i)的稠浆料稀释形成稀浆料，
iii)将步骤ii)的稀浆料在金属丝上排水形成网，及
iv)将步骤iii)的网干燥形成纸或纸板，
其中步骤(i)的纤维素稠浆料包含有机聚合物微粒。
有机聚合物微粒可以是非离子的、阳离子的或阴离子的。优选，有机聚合物微粒是阳离子的或阴离子的。更优选，有机聚合物微粒是阴离子的。有机聚合物微粒基本上是水不溶性的。在未溶涨的状态下，有机聚合物微粒的数均颗粒直径可小于1000nm，优选小于750nm，更优选小于300nm。
优选，有机聚合物微粒由烯属不饱和单体形成。
烯属不饱和单体的实例有丙烯酸单体例如(甲基)丙烯酸及其盐、2-丙烯酰胺基-2-甲基-1-丙磺酸及其盐、(甲基)丙烯酰胺、N-C1-4-烷基(甲基)丙烯酰胺、N，N-二(C1-4-烷基)(甲基)丙烯酰胺、C1-4-烷基(甲基)丙烯酸酯、[N，N-二(C1-4-烷基)氨基]C1-6-烷基(甲基)丙烯酸酯及其C1-4-烷基卤化物加合物、[N，N-二(C1-4-烷基)氨基]C1-6-烷基(甲基)丙烯酰胺及其C1-4-烷基卤化物加合物或丙烯腈、苯乙烯单体例如苯乙烯或4-苯乙烯磺酸及其盐、乙烯基单体例如乙酸乙烯酯或N-乙烯基吡咯烷酮、烯丙基单体例如氯化二烯丙基二甲基铵或氯化四烯丙基铵、烯烃单体例如乙烯、丙烯或丁二烯，及马来酸单体例如马来酸及其盐、马来酸酐或马来酰亚胺。各酸的盐可以是例如铵盐或碱金属盐例如钠盐。
非离子有机聚合物微粒可以仅由非离子烯属不饱和单体形成或由非离子、阴离子和阳离子烯属不饱和单体形成或由阴离子和阳离子烯属不饱和单体形成，条件是总的阳离子电荷为零。阳离子有机聚合物微粒可以由阳离子及任选非离子和/或阴离子单体形成，条件是总电荷为正。阴离子有机聚合物微粒可以由阴离子及任选非离子和/或阳离子单体形成，条件是总电荷为负。优选，阴离子有机聚合物微粒由阴离子和非离子烯属不饱和单体形成。
更优选，有机聚合物微粒由丙烯酸单体形成，最优选，由包含至少一种丙烯酸阴离子单体和至少一种丙烯酸非离子单体的丙烯酸单体形成。
丙烯酸阴离子单体的实例有(甲基)丙烯酸、2-丙烯酰胺基-2-甲基-1-丙磺酸及其盐。优选的丙烯酸阴离子单体是(甲基)丙烯酸及其盐。更优选的阴离子单体是丙烯酸及其盐。
丙烯酸非离子单体的实例有(甲基)丙烯酰胺、N-C1-4-烷基(甲基)丙烯酰胺例如N-甲基(甲基)丙烯酰胺、N，N-二(C1-4-烷基)(甲基)丙烯酰胺例如N，N-二甲基(甲基)丙烯酰胺、C1-4-烷基(甲基)丙烯酸酯例如(甲基)丙烯酸甲酯和丙烯腈。优选，丙烯酸非离子单体是(甲基)丙烯酰胺。更优选，它是丙烯酰胺。
丙烯酸阴离子单体/丙烯酸非离子单体的重量比可以是99/1-1/99。优选，它是90/10-10/90，更优选80/20-20/80，及最优选70/30-50/50。
优选，聚合物微粒在交联剂的存在下形成。优选，使用基于单体的至少4摩尔ppm交联剂。交联剂的量优选在4-6000摩尔ppm之间，更优选，在10-2000摩尔ppm之间，及更优选，在20-500摩尔ppm之间。交联剂的实例有N，N-亚甲基双丙烯酰胺、聚(乙二醇)-二甲基丙烯酸酯、四烯丙基氯化铵及邻苯二甲酸二烯丙酯。优选的交联剂是N，N-亚甲基双丙烯酰胺。
有机聚合物微粒的溶液粘度可以是1.0-2.0mPas。
有机聚合物微粒可以用本领域已知的技术通过单体的微乳液聚合制备。例如，有机聚合物微粒可以通过一种方法制备，该方法包括(i)将包含单体水溶液的水相加入到包含烃类液体和表面活性剂或表面活性剂混合物的油相中，形成小水滴在该油相中的反相(inverse)微乳液，及(ii)在引发剂或引发剂混合物的存在下将单体聚合，形成包含聚合物微粒的微乳液。
该水相可包含其他添加剂例如交联剂、螯合剂例如二亚乙基三胺五乙酸、五钠盐或pH调节剂例如无机或有机酸或碱。水相也可包含引发剂或引发剂混合物(或部分)。
烃类液体可由一种或多种液体烃组成，例如甲苯、己烷、石蜡油或矿物油。水相/油相的重量比通常在1/4-4/1的范围内，优选在1/2-2/1的范围内。
通常选择一种或多种表面活性剂以获得范围在8-约11的HLB(亲水亲油平衡)值。除了适当的HLB值外，表面活性剂的浓度也必须小心地选择以获得反相微乳液。典型的表面活性剂有倍半油酸脱水山梨醇酯和六油酸聚氧化乙烯山梨醇酯。
通常在与油相混合之前将引发剂或引发剂混合物加入到水相中。或者，可将部分引发剂加入到水相中及将部分引发剂加入到在将水相与油相混合之后获得的微乳液中。引发剂可以是过氧化物例如过氧化氢或叔丁基氢过氧化物、过硫酸盐例如过硫酸钾、偶氮化合物例如2，2-偶氮二异丁腈或由氧化剂和还原剂组成的氧化还原对。氧化剂的实例有过氧化物和过硫酸盐。还原剂的实例有二氧化硫和硫酸亚铁铵。
任选在聚合反应期间可存在链转移剂例如巯基乙酸、次磷酸钠、2-巯基乙醇或N-十二烷基硫醇。
任选，有机聚合物微粒可通过汽提从微乳液中分离。另外，有机聚合物微粒可任选分离后干燥。有机聚合物微粒可以再分散在水中用于造纸。
或者，也可将包含聚合物微粒的微乳液直接分散在水中。取决于用于微乳液中的表面活性剂的类型和量，在水中分散可能需要使用具有高HLB值的表面活性剂。
纤维素稠浆料可以由木质纸浆制备，该木质纸浆一般来自软木树例如云杉、松树、枞树、落叶松和铁杉，但是也可来自某些硬木树例如桉树和桦树。木质纸浆可以是化学纸浆例如牛皮纸纸浆(硫酸盐纸浆)、机械纸浆例如研磨木材、热机械或化学热-机械纸浆或回收纸浆。纸浆也可以是化学、机械和/或回收纸浆的混合物。纸浆可以用氧、臭氧或过氧化氢漂白。
稠浆料的固体含量通常在0.5-5％的范围内，优选，1.0-4％，更优选，1.5-3.5％重量，最优选2.5-3.5％重量。
稀浆料通过用水稀释稠浆料形成并且固体含量的范围通常在0.1-2％，优选，0.3-1.5％，更优选，0.5-1.5％重量。
各种添加剂例如填料、阳离子凝结剂、干强度剂、保持助剂、胶粘剂、荧光增白剂及干固定剂可以加入到湿端部分的浆料中。加入的顺序和特定的加入点取决于具体的应用，并且是普通造纸实践。
填料的实例有矿物硅酸盐例如滑石、云母和粘土例如高岭土，碳酸钙例如磨细的碳酸钙(GCC)和沉淀碳酸钙(PCC)，及二氧化钛。所添加的填料的量可基于最终纸干重最大到60％重量。通常将填料加入到稠浆料中。
阳离子凝结剂是具有相对高阳离子电荷的水溶性低分子量化合物。阳离子凝结剂可以是无机化合物例如硫酸铝、硫酸铝钾(明矾)或聚氯化铝(PAC)或有机聚合物例如聚二烯丙基二甲基氯化铵、聚酰胺基胺/表氯醇缩合物或聚乙烯亚胺。阳离子凝结剂也通常加入到稠浆料中并起固定树脂(pitch)和/或粘性作用。
阳离子凝结剂，它们是有机聚合物，也可以加入以中和浆料的电荷，它们可能是需要的，例如在相对高分子量的阴离子保持助剂随后加入到稀浆料中时。在该情况下，阳离子凝结剂通常非常接近于稀释点加入使稠浆料制成稀浆料。
干强度剂的实例有相对低分子量(通常在1百万克/摩尔以下)的丙烯酰胺与相对高分子量的多糖的水溶性阴离子共聚物。丙烯酰胺的阴离子共聚物的实例有由丙烯酰胺和阴离子单体例如丙烯酸衍生的共聚物。通常将丙烯酰胺的阴离子共聚物加入到稀浆料中。多糖的实例有羧甲基纤维素、瓜尔胶衍生物和淀粉。阳离子淀粉、羧甲基纤维素和瓜尔胶衍生物通常加入到稠浆料中，而未煮过的天然淀粉可以喷到形成的网上。
优选，将保持助剂加入到湿端部分中，以改善细料、填料和纤维在网上的保持。保持助剂的实例有水溶性聚合物、阴离子无机微粒、聚合物有机微粒及其组合(保持系统)。在风扇式泵之后，保持助剂通常加入到稀浆料中。
用作保持助剂的水溶性聚合物可以是非离子的、阳离子的或阴离子的。非离子聚合物的实例有聚环氧乙烷和聚丙烯酰胺。阳离子聚合物的实例有衍生自丙烯酰胺和阳离子单体例如N，N-二烷基氨基烷基(甲基)丙烯酸酯的烷基卤化物加合物，例如N，N-二甲基-氨基乙基丙烯酸酯甲基氯化物的共聚物。阴离子聚合物的实例有衍生自丙烯酰胺和阴离子单体例如丙烯酸或2-丙烯酰胺基-2-甲基-1-丙磺酸的共聚物。优选，用作保持助剂的阴离子聚合物是相对高分子量的(通常在1百万克/摩尔以上)。
阴离子无机微粒的实例有胶体二氧化硅和膨胀粘土例如膨润土。聚合物有机微粒的实例如上所述。
可以将两种或多种保持助剂组合形成保持系统。
保持系统的实例有阴离子水溶性聚合物和阴离子无机微粒的组合及阳离子水溶性聚合物、阴离子水溶性聚合物和阴离子无机微粒的组合。当阴离子水溶性聚合物与阴离子无机微粒组合加入时，这两种组分可以同时加入，或者先加入阴离子无机微粒，接着加入聚合物。当保持系统也包含阳离子水溶性聚合物时，该阳离子聚合物通常在加入阴离子水溶性聚合物和阴离子无机微粒之前加入。
保持系统的其他实例有阳离子水溶性聚合物与聚合物有机微粒的组合及阳离子水溶性聚合物、阴离子水溶性聚合物和聚合物有机微粒的组合。
优选，保持助剂是阳离子水溶性聚合物或者是包含阳离子水溶性聚合物的保持系统。
胶粘剂的实例有天然胶粘剂例如松香和合成胶粘剂例如烯基琥珀酸酐(ASA)和烷基烯酮二聚体(AKD)。荧光增白剂的实例有例如以商品名
CBS-X销售的1，2-二苯乙烯衍生物。
在加入其他稠浆料添加剂之前或之后或之间，可以将有机聚合物微粒加入到稠浆料中。
有机聚合物微粒可以以固体形式或作为水性分散体加入。通常，有机聚合物微粒以固体含量在1％以下(重量)的水性分散体加入。
通常，加到稠浆料中的有机聚合物微粒的量为基于该浆料干重的50-5000ppm，优选100-3000ppm，更优选300-2000ppm，及最优选400-1000ppm(重量)。
当有机聚合物微粒作为保持助剂另外加入到稀浆料中时，加入到稀浆料中的有机聚合物微粒的量的范围为基于该浆料干重的50-5000ppm，优选100-3000ppm，更优选300-2000ppm，及最优选300-1000ppm(重量)。
本发明的另一部分是可通过本发明的方法获得的纸或纸板。
本发明的另一部分是用于提高纸或纸板的强度，特别是内部粘合强度以及湿网强度的方法，该方法包括将有机聚合物微粒加入到稠浆料中。
本发明制备纸或纸板的方法的优势是，将有机聚合物微粒加入到稠浆料中显著地改善了湿网强度，因此相应地改善了压榨部分和干燥器部分机器的运转能力。
本发明的方法的另一个优势是，为了获得高干强度，特别是高内部粘合强度的纸，在湿端部分中不加入淀粉或仅加入少量淀粉是必需的。因此，由于需要更少的加入步骤，因此整个方法更容易。特别是现在可以避免将淀粉喷在网上，那通常导致运转能力问题。另外，湿端部分中收集的白水不含淀粉或者仅含少量淀粉。由于白水中淀粉的存在通常导致细菌的过量生长和粘液的形成，这需要加入大量的生物杀灭剂，不存在淀粉或少量淀粉的存在意味着粘液形成的减少及仅需要少量生物杀灭剂。
图1概述了用于在造纸厂制备纸或纸板的本发明方法。
实施例
实施例1
有机聚合物微粒的制备
有机聚合物微粒由重量比为40/60的丙烯酰胺/丙烯酸(为48％重量的丙烯酸铵)，在基于所有单体的53摩尔ppm亚甲基双丙烯酰胺的存在下，根据EP 0 462 365A1中第9页第14-38行的“制备阴离子微乳液的方法”的类似方法制备，不同之处在于氢氧化钠由氢氧化铵代替。
实施例2
以接近320m/min的速度，用制备10-11t/h纸的长网造纸机制备100g/m2的包装板。
湿端部分见图1中所示，进一步的解释如下：制备含3.2％重量纤维(12％针法漂白的(Needle Bleached)牛皮纸浆和88％叶法漂白的(Leaf Bleached)牛皮纸浆)的稠浆料，并搅打到390-420ml加拿大标准，即基于纤维干重的20％重量沉淀碳酸钙(PCC)。向该含有纤维和填料及固体含量为3.2％重量的稠浆料中，加入711ppm(重量)实施例1中的有机聚合物微粒、0.45％重量荧光增白剂(OB)、0.9％重量烯基烯酮二聚体(AKD)和0.015％重量聚氯化铝(PAC)，全部基于纤维干重。在风扇式泵之前，用白水将该稠浆料稀释到0.6-0.7％重量固体含量，形成稀浆料。通过机器筛网、最后高剪切的步骤后，再加入633ppm(重量)实施例1的有机聚合物微粒。然后将该稀浆料通过压头箱装载到金属丝上。
第一遍保持(retention)是82.3，灰分第一遍保持是66.0。
比较实施例1
重复实施例1的方法，但是不将有机聚合物微粒加入到稠浆料中，而且是1200，而不是633ppm(重量)聚合物微粒在压头箱前不久加入到稀浆料中。另外，将0.8％重量
40041(一种阳离子淀粉)加入到该稠浆料中，在形成板之后不久，将0.6％重量天然淀粉喷到湿网上，该湿网为第一个排水元件，在尖的向上抛物线型喷淋器中。淀粉以基于所有造纸原料的干重计的％重量给出。
测试结果：
纸或纸板的内部粘合强度是当通过纸的厚度即在纸片的Z方向上施加拉伸载荷时，该产品抵抗裂开的能力，是该纸或纸板的内部强度的度量。实施例1中获得的包装板和比较实施例1中获得的包装板的内部粘合强度用Scott粘合力试验仪测定。
| 加到稠浆料中的淀粉[％] | 喷到网上的淀粉[％] | 加到稠浆料中的OPM1[ppm] | 压头箱前加入的OPM1[ppm] | 内部粘合强度[J/m2] | 形成 | |
| 实施例2 | 0 | 0 | 711 | 633 | 194.8 | 86.2 |
| 比较实施例1 | 0.5 | 0.6 | 0 | 1200 | 175.0 | 89. |
表1.1有机聚合物微粒
从表1中可以看出，当有机聚合物微粒不仅仅在最后剪切步骤之后和在压头箱之前加入，而是部分有机聚合物微粒也加到稠浆料中时，内部粘合强度及因此导致的纸内部粘合强度增加。甚至更意外的是，分开加入有机聚合物微粒允许完全省略淀粉。两种方法中的形成类似。
另外，与比较实施例1的方法相比，实施例2的方法中的湿网强度显著增加。
Claims (8)
1.一种制备纸或纸板的方法，所述方法包括步骤
i)提供纤维素的稠浆料，
ii)将步骤i)的稠浆料稀释形成稀浆料，
iii)将步骤ii)的稀浆料在金属丝上排水形成网，及
iv)将步骤iii)的网干燥形成纸或纸板，
其中步骤(i)的纤维素稠浆料包含有机聚合物微粒。
2.权利要求1的方法，其中所述有机聚合物微粒是阳离子的或阴离子的。
3.权利要求1或2的方法，其中所述有机聚合物微粒是阴离子的。
4.权利要求1-3中任一项的方法，其中微粒由烯属不饱和单体形成。
5.权利要求1-4中任一项的方法，其中所述有机聚合物微粒由丙烯酸单体形成。
6.权利要求1-5中任一项的方法，其中所述聚合物微粒在交联剂的存在下形成。
7.纸，所述纸可通过权利要求1-6中任一项的方法获得。
8.一种提高纸或纸板的强度，特别是内部粘合强度和湿网强度的方法，所述方法涉及将有机聚合物微粒加入到稠浆料中。
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| CN103210145A (zh) * | 2010-11-15 | 2013-07-17 | 凯米罗总公司 | 用于增加纸产品的干态强度的组合物和方法 |
| CN104562847A (zh) * | 2014-12-17 | 2015-04-29 | 广西大学 | 一种提高纸张强度的方法 |
| CN105077556A (zh) * | 2015-07-09 | 2015-11-25 | 川渝中烟工业有限责任公司 | 一种提高造纸法再造烟叶中碳酸钙留着率的方法 |
| CN111386289A (zh) * | 2017-09-08 | 2020-07-07 | 索理思科技开曼公司 | 包含交联的阴离子有机聚合微粒的组合物、其制备方法及在纸张和纸板制造方法中的用途 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103210145A (zh) * | 2010-11-15 | 2013-07-17 | 凯米罗总公司 | 用于增加纸产品的干态强度的组合物和方法 |
| CN103210145B (zh) * | 2010-11-15 | 2016-05-25 | 凯米罗总公司 | 用于增加纸产品的干态强度的组合物和方法 |
| CN104562847A (zh) * | 2014-12-17 | 2015-04-29 | 广西大学 | 一种提高纸张强度的方法 |
| CN105077556A (zh) * | 2015-07-09 | 2015-11-25 | 川渝中烟工业有限责任公司 | 一种提高造纸法再造烟叶中碳酸钙留着率的方法 |
| CN105077556B (zh) * | 2015-07-09 | 2017-03-01 | 川渝中烟工业有限责任公司 | 一种提高造纸法再造烟叶中碳酸钙留着率的方法 |
| CN111386289A (zh) * | 2017-09-08 | 2020-07-07 | 索理思科技开曼公司 | 包含交联的阴离子有机聚合微粒的组合物、其制备方法及在纸张和纸板制造方法中的用途 |
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| US20120067535A1 (en) | 2012-03-22 |
| EP2087172B1 (en) | 2017-08-23 |
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| NZ575263A (en) | 2012-02-24 |
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| US8088251B2 (en) | 2012-01-03 |
| RU2009119355A (ru) | 2010-11-27 |
| BRPI0717984B1 (pt) | 2020-11-10 |
| US20100288457A1 (en) | 2010-11-18 |
| EP2087172A1 (en) | 2009-08-12 |
| MX2009004481A (es) | 2009-05-12 |
| WO2008049748A1 (en) | 2008-05-02 |
| BRPI0717984A2 (pt) | 2013-11-12 |
| NO20091974L (no) | 2009-05-25 |
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