CN1312871A - 提高造纸中滤水速度和细小纤维留着率的方法 - Google Patents

提高造纸中滤水速度和细小纤维留着率的方法 Download PDF

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CN1312871A
CN1312871A CN99809766A CN99809766A CN1312871A CN 1312871 A CN1312871 A CN 1312871A CN 99809766 A CN99809766 A CN 99809766A CN 99809766 A CN99809766 A CN 99809766A CN 1312871 A CN1312871 A CN 1312871A
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弗兰克·J·苏特曼
理查德·A·霍比克
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Abstract

本发明公开了一种在无硅石/皂土型微粒的不加填的新闻纸型配料中有效的,提高滤水速度和细小纤维留着率的方法。该方法包括加入阳离子或两性淀粉和阳离子聚合电解质,而后加入高分子量阴离子聚丙烯酰胺共聚物。

Description

提高造纸中滤水速度和细小纤维留着率的方法
发明领域
本发明涉及纸张或纸板的生产，特别是一种在新闻纸、名录纸纸浆、磨木浆特种纸浆的成形中提高基于机械木浆的配料的留着率和/或滤水性能的方法。
发明背景
纸张的生产包括一纸幅纤维素纤维和任选的填料的成形和脱水，通常在能够改良终产品或造纸生产的添加剂的存在下进行。许多等级的纸张包括较高水平的无机填料如高岭石、碳酸钙和二氧化钛。例如，优质纸张通常被称为高级纸张，可以从高级漂白化学浆制得，可以含干纸重5-35％的无机填料。在这种纸张的生产中，使用助留剂和助滤剂是常见的。一段时间以来，这种助留剂和助滤剂被证明在加填料的纸张或高级纸张的生产中是低成本并有效的。
但是，非常大量的纸张生产是基本上不加填的。例如，新闻纸的生产。不加填的纸张基本上不含填料，并通常不向制备纸张的纸浆中故意加入填料。在过去的几年中，在新闻纸和其它级别的含机械木浆的纸张的生产中使用助留剂变得日益常见。最常见的处理是阳离子聚丙烯酰胺、聚环氧乙烷和聚乙烯亚胺。
美国专利第4,305,781号公开了一种增加基本上不加填的纸张的滤水和留着率的方法，包括在悬浮液中水溶性高分子量基本上非离子的聚合物和皂土型白土的组合。
在“新闻纸纸浆系中的聚合物凝聚剂在增强细小纤维留着率中的应用”(“Application of Polymeric Flocculant in Newsprint StockSystem for Fines Retention Improvement”),C.H.Tay,Tappi,Volume63,No.6,June 1980中公开了高分子量的非离子聚环氧乙烷使新闻纸纸浆中细小纤维留着的效力。该文章还指出阴离子助留剂倾向于削弱纸浆的滤水性能。
在“增强新闻纸质量的助留剂”(“Retention Aids for QualityImprovements in Newsprint”),D.S.Honig,1988年造纸工作者会议(1988 Paper Makers Conference)219中指出，基于大量新闻纸助留剂的研究文章，总的结论是常规聚丙烯酰胺(作为单一或复合组分系)是无效的或不经济的。该文章继续讨论了在新闻纸生产中作为助留剂的阳离子聚丙烯酰胺和双组分低分子量阳离子聚合物/低pKa阴离子聚丙烯酰胺处理方法的使用。作者得出结论，与其它处理相比，阳离子聚丙烯酰胺更不复杂，同样或更为有效，特别是在更低用量水平有效。
在使用阴离子聚丙烯酰胺的显示增强滤水和细小纤维留着率的处理方法中，硅酸盐(如胶态硅石或聚硅酸盐微胶)或皂土是必需组分。参见例如，美国专利第4,643,801、5,584,966和5,595,630号。
发明概述
本发明者发现了一种对无硅石/皂土型微粒的新闻纸型配料有效的新型助滤和助留剂处理方法。本发明的新型助留和助滤剂处理方法包括以下物质的顺序或协同加入：(ⅰ)阳离子或两性淀粉；和(ⅱ)阳离子聚合电解质；而后加入高分子量阴离子聚丙烯酰胺。发明详述
本发明涉及一种用于纸张生产的方法，该方法提供在纸张配料的成形和脱水中的快速滤水和细小纤维的良好留着率。本发明涉及在从含机械木浆的基本上不加填的配料制得的纸张的成形中增强的滤水和细小纤维留着率。这指得是纸张如新闻纸、名录纸和磨木浆特种纸张。不加填的纸张基本上不含填料，通常含低于干纸重量5％的填料，且通常不向制备纸张或纸板的纸浆中故意加入填料。该纸张通常含有作为配料组分的回用废纸，该回用废纸可能在制得的纸页中掺入少量(＜5％)的填料。
本发明涉及一种用于不加填的纸张加工的添加剂组合，该添加剂组合增强滤水和细小纤维留着率。本发明的添加剂组合基本上不含微粒处理物料如硅石、聚硅酸盐、聚硅酸盐微胶，以及白土如皂土。本文中使用的术语“基本上不含”是指尽管可能存在微量的这类物料，但是它们不是被故意加入的，并且它们对达到本发明的处理组合的功效不是必需的。
本发明的处理组合包括：阴离子高分子量聚丙烯酰胺、阳离子或两性淀粉以及有机或无机阳离子聚合电解质。本发明的处理组合加入不加填的纸浆配料的量(前提是使产物有效)是每吨约2.5至20磅淀粉，每吨约0.25至1磅阳离子有机聚合电解质，或每吨约5磅无机阳离子聚合电解质，以及每吨0.25至0.75磅高分子量阴离子聚丙烯酰胺。使用该处理组合时，淀粉和阳离子聚合电解质的加入顺序是可以颠倒的，尽管先加入淀粉是优选的。淀粉和阳离子聚合电解质都必须在阴离子聚丙烯酰胺之前加入。
本发明的处理组合的淀粉组分可以是臼齿形玉米、糯玉米、或马铃薯淀粉，且是阳离子或两性性质的。淀粉上的季铵取代度优选在0.1-0.4％之间，最优选为约0.3-0.4％之间。
本发明的处理组合的阳离子聚合电解质组分可以是有机性质的，如表氯醇-二甲胺(EPI-DMA)缩合物聚合物、EPI-DMA-乙二胺(EDA)缩聚物、氯化二烯丙基二甲基铵(聚DADMAC)、聚乙烯-亚胺，或基于聚酰胺型胺类的材料。它也可以是无机性质的，如明矾、聚氯化铝或其它基于铝的化合物。
本发明的高分子量阴离子丙烯酰胺优选是基本上线性的丙烯酰胺/丙烯酸钠共聚物。其它阴离子丙烯酰胺共聚物如2-丙烯酰胺-2-甲基丙烷磺酸(AMPS,Lubrizol的注册商标)也有效。高分子量是指分子量优选大于1,000,000，最优选大于约10,000,000。阴离子丙烯酰胺组分的阴离子电荷的摩尔百分比可以在约20-70％的范围内，摩尔百分比30％的负电荷材料是特别有效的。
以下通过一些具体的实施例对本发明作进一步的描述，这些实施例仅被视为说明性的而不限制本发明的范围。
实施例
以下实施例中的数据是通过使用实验室滤水设备，使用实验室制备的75％磨石磨木浆/25％漂白针叶硫酸盐浆配料得到的。该滤水设备通过40目网在真空影响下将纸浆滤水。真空贮水池的设定值在整个试验中保持恒定，但是网下的真空水平作为滤水速度、网的气流阻力以及成形衬垫的气流阻力的函数而变化。同时，网下的旋转薄片提供对成形纸张的压力脉冲。滤水速度和真空水平数据是在滤水过程期间采集的，滤水过程通常持续仅几秒钟。网上的目标保留定量是机上控制的定量(对新闻纸为每平方米48克)。达到定量目标所需的纤维量包含于250克稀纸浆样品中。滤水完成后，将真空继续施加于形成的衬垫一段固定的时间。这使得平衡真空水平得以被确定。
三种反应变量被用于评价所试验的处理方法的有效性。校正滤水时间(CDT)是基于从试验开始至已发生90％的滤水(225克滤液已通过网)的点之间的越时。由于实际绝干衬垫质量和目标间的差别，使用线性校正调节原滤水时间。首过细小纤维留着率(FPFR)是基于保留的衬垫的绝干质量和原始纸浆干重以及细小纤维含量并通过常规方式计算。网下的腔的真空水平刚好在气/水界面穿透网之前达到最大。这一最大值与平衡真空的比值被定义为峰对平衡真空比(PEVR)。已证明PEVR与纸页成形的化学处理方法的效果有关。低PEVR预示较好的纸页成形。CDT和PEVR所基于的数据是通过高速数据采集系统得到的。试验以每种条件平行五份的方式进行以增强数据的精密度。
实施例1
表1总结了有或无胶态硅石的阳离子淀粉/明矾(阳离子聚合电解质)/阴离子聚丙烯酰胺处理顺序的结果。另外，阳离子淀粉和明矾的加入顺序被颠倒。还给出了明矾被EPI/DMA/EDA缩聚物代替时的对照。表1中所用的物质如下：可溶于冷水的阳离子取代度为摩尔百分比0.3％的两性马铃薯淀粉；ANPAM，一种具有摩尔百分比30％丙烯酸钠/丙烯酰胺比的高分子量聚丙烯酰胺。表1中，所有列于括号的用量都是每吨中活性物质的磅数。为对照目的，进行未处理的对照和EPI/DMA/EDA凝结剂加阳离子聚丙烯酰胺常规双阳离子处理程序。
               表1处理               CTD(Sec.) FPFR％    PEVR淀粉(20)/明矾(5)/    2.46   17.19     1.49ANPAM(0.5)/胶态硅石(2)淀粉(20)/明矾(5)     2.52   17.96     1.50/ANPAM(0.5)明矾(5)/淀粉(20)/    2.49   23.66     1.42ANPAM(0.5)淀粉(20)/EPI/DMA/EDA 2.48   18.35     1.47(0.5)/ANPAM(0.5)未处理对照           3.00   -5.25     1.88
表1中的数据显示从阳离子淀粉/阳离子聚合电解质/阴离子高分子量聚丙烯酰胺处理中除去胶态硅石并未引起滤水时间、细小纤维留着率和PEVR的显著变化。对在这种处理中胶态硅石或其它微粒物料是必需的，且阴离子聚丙烯酰胺不利于作为新闻纸助留剂的先前技术而言这是令人吃惊的。该数据还显示有机聚合电解质可以被明矾代替，这并不显著影响结果，但它可以仅以明矾用量的10％而被使用。表1中，未处理的对照的FPFR的负值是与用于常规纸浆细小纤维筛分的筛相比相对粗的网的结果。这说明在本试验系列中在网上的纸浆留着难于任何Britt细小纤维筛分罐。
实施例2
表2中，试验如表1中总结的一样，被用一批第二次单独制备的配料重复。另外，进行了淀粉、ANPAM和明矾的独立试验。
                      表2处理                      CTD(Sec.)  FPFR％    PEVR淀粉(20)/明矾(5)/           3.06     22.99     1.10ANPAM(0.5)/胶态硅石(1)淀粉(20)/明矾(5)            3.05     24.26     1.11/ANPAM(0.5)明矾(5)/淀粉(20)/           3.18     22.29     1.09ANPAM(0.5)淀粉(20)/EPI/DMA/EDA        3.18     22.80     1.15(0.5)/ANPAM(0.5)淀粉(20)/ANPAM(0.5)         3.63     15.22     1.20EPI/DMA/EDA(0.5)/ANPAM(0.5) 3.77     13.38     1.15淀粉(20)                    3.60     13.00     1.09明矾(5)                     4.34      2.05     1.19ANPAM(0.5)                  4.77      0.84     1.28未处理对照                  5.43     -0.90     1.34实施例3
表3中，进行了评价阳离子淀粉用量的影响的试验。数据显示当成形指示剂保持相对恒定时，滤水和留着率反应对淀粉用量有显著的灵敏度。
                     表3处理                       CTD(Sec.)   FPFR％   PEVR淀粉(20)/EPI/DMA/EDA(0.5)/   3.18      22.80    1.15ANPAM(0.5)EPI/DMA/EDA(0.5)/淀粉(20)    3.22      22.89    1.14/ANPAM(0.5)淀粉(10)/EPI/DMA/EDA(0.5)/   3.26      18.57    1.13ANPAM(0.5)EPI/DMA/EDA(0.5)/淀粉        3.44      18.18    1.15(10)/ANPAM(0.5)淀粉(5)/EPI/DMA/EDA          3.38      16.84    1.15(0.5)/ANPAM(0.5)EPI/DMA/EDA(0.5)/淀粉(5)/    3.47      17.84    1.16ANPAM(0.5)淀粉(0)/EPI/DMA/EDA(0.5)/    3.77      13.38    1.15ANPAM(0.5)EPI/DMA/EDA(0.5)/淀粉(0)/    3.77      13.38    1.15ANPAM(0.5)
实施例4
表4中，研究了阳离子聚合电解质的用量对本发明的组合的影响。
                        表4处理                            CTD(Sec.)   FPFR％   PEVR淀粉(20)/EPI/DMA/EDA(1.0)/        3.03      23.54    1.10ANPAM(0.5)淀粉(20)/EPI/DMA/EDA(0.75)/       3.12      20.21    1.12/ANPAM(0.5)淀粉(20)/EPI/DMA/EDA(0.5)/        3.18      22.80    1.15ANPAM(0.5)淀粉(20)/EPI/DMA/EDA(0.25)/       3.22      26.80    1.15ANPAM(0.5)淀粉(20)/EPI/DMA/EDA              3.63      15.22    1.20(0)/ANPAM(0.5)
实施例5
表5中，试验了在本发明的组合以及类似的包含胶态硅石的组合中阴离子高分子量聚丙烯酰胺的用量的影响。
                     表5处理                        CTD(Sec.)  FPFR％    PEVR淀粉(20)明矾(5)/ANPAM(0.75)   3.02      26.42    1.18淀粉(20)/明矾(5)/ANPAM(0.75)/ 2.90      25.48    1.14胶态硅石(2)淀粉(20)/明矾(5)/ANPAM(0.5)   3.05      24.26    1.11淀粉(20)/明矾(5)/ANPAM(0.5)/  3.06      22.99    1.10胶态硅石(1)淀粉(20)/明矾(50)/ANPAM(0.25) 3.22      19.24    1.09淀粉(20)/明矾(5)/ANPAM(0.25)/ 3.04      22.19    1.12胶态硅石(2)实施例6
在表6(B)中，评价了多种阴离子高分子量聚丙烯酰胺聚合物。所试验的所有这一类型的聚合物都是有效的。具有摩尔百分比20-40％阴离子范围的产物对处理B是最优选的。表6(A)总结了所试验的阴离子聚合物的性质。
            表6(A)处理 形式  摩尔％AA  相对分子量(106)A    粉末    20        11B    乳剂    30        21C    粉末    30        12D    乳剂    30        21E    粉末    30        18F    乳剂    40        23G    粉末    40        18H    粉末    70        15I    粉末    100        6
                 表6(B)处理                            CTD(Sec.)   FPFR％   PEVR淀粉(20)/EPI/DMA/EDA(0.5)/A(0.5)  3.26      19.22    1.16淀粉(20)/EPI/DMA/EDA(0.5)/B(0.5)  3.03      23.54    1.10淀粉(20)/EPI/DMA/EDA(0.5)/C(0.5)  3.27      15.32    1.14淀粉(20)/EPI/DMA/EDA(0.5)/D(0.5)  3.31      18.23    1.20淀粉(20)/EPI/DMA/EDA(0.5)/E(0.5)  3.23      19.61    1.16淀粉(20)/EPI/DMA/EDA(0.5)/F(0.5)  3.17      23.48    1.12淀粉(20)/EPI/DMA/EDA(0.5)/G(0.5)  3.34      17.76    1.14淀粉(20)/EPI/DMA/EDA(0.5)/H(0.5)  3.37      13.24    1.19淀粉(20)/EPI/DMA/EDA(0.5)/I(0.5)  3.44       9.66    1.22实施例7
在表7(B)中，试验了在本发明的组合中各种有机阳离子聚合电解质材料的用量的影响。所试验的所有材料都有效。表7(A)总结了所试验的有机阳离子聚合电解质的性质。
          表7(A)处理    描述J       支链EPI/DMA/EDA缩合物K       线性EPI/DMA缩合物-低分子量L       线性EPI/DMA缩合物-高分子量M       聚二氯二烯丙基二甲基铵
    (DADMAC)-低分子量N       聚氯化二烯丙基二甲基铵-高分子量O       聚酰胺多胺表氯醇缩合物P       聚乙烯亚胺
               表7(B)处理                      CTD(Sec.)  FPFR％   PEVR淀粉(5)/J(0.5)/ANPMA(0.5)    3.04    10.97   1.18淀粉(5)/K(0.5)/ANPMA(0.5)    3.25    10.79   1.23淀粉(5)/L(0.5)/ANPMA(0.5)    3.21     9.46   1.25淀粉(5)/M(0.5)/ANPMA(0.5)    3.15    13.58   1.22淀粉(5)/N(0.5)/ANPMA(0.5)    3.16    14.57   1.27淀粉(5)/O(0.5)/ANPMA(0.5)    3.40     9.35   1.28淀粉(5)/P(0.5)/ANPMA(0.5)    3.05    22.33   1.24
实施例8
在表8(B)中，试验了本发明的组合中各种改性淀粉的效果。所试验的所有淀粉都有效。一般而言，取代更多的淀粉是优选的。表8(A)总结了所试验的市场上有售的淀粉的性质。
                      表8(A)处理   来源         阳离子取代  离子官  阴离子取代  离子官
                度(Mole％)  能团    度(Mole％)  能团Q    马铃薯-可溶     0.30       季铵     未知       磷酸盐
 于冷水R    臼齿形玉米      0.20       季铵      0S    臼齿形玉米      0.28       季铵      0T    臼齿形玉米      0.35       季铵      0U    糯玉米          0.18       季铵      0V    糯玉米          0.28       季铵      0W    糯玉米          0.35       季铵      0X    马铃薯          0.18       季铵      0.3        磷酸盐Y    马铃薯          0.28       季铵      0.3        磷酸盐Z    马铃薯          0.35       季铵      0.3        磷酸盐
                    表8(B)处理                     CTD(Sec.)   FPFR％   PEVRQ(10)/J(0.5)/ANPMA(0.5)    3.03      17.71    1.25R(10)/J(0.5)/ANPMA(0.5)    3.00      20.82    1.24S(10)/J(0.5)/ANPMA(0.5)    3.02      16.49    1.32T(10)/J(0.5)/ANPMA(0.5)    2.96      21.39    1.22U(10)/J(0.5)/ANPMA(0.5)    2.97      17.58    1.24V(10)/J(0.5)/ANPMA(0.5)    3.08      17.41    1.23W(10)/J(0.5)/ANPMA(0.5     2.94      22.87    1.22X(10)/J(0.5)/ANPMA(0.5)    3.05      14.13    1.25Y(10)/J(0.5)/ANPMA(0.5)    3.02      17.44    1.25Z(10)/J(0.5)/ANPMA(0.5)    2.94      22.64    1.22

Claims (8)

1．一种在基本上不含硅石和/或皂土的造纸方法中，提高用基于机械木浆的基本上不含填料的配料造纸时的滤水速度和细小纤维留着率，同时保留纸页成形性质的方法，包括以下步骤：
A．向含有纸浆的含水纸张配料中顺序或一起加入：
(ⅰ)．阳离子或两性淀粉；以及
(ⅱ)．阳离子聚合电解质；此后
B．向含有纸浆和所述阳离子或两性淀粉以及阳离子聚合电解质的所述含水纸张配料中加入高分子量阴离子丙烯酰胺共聚物。
2．如权利要求1所述的方法，其中所述阳离子或两性淀粉选自由马铃薯淀粉、臼齿形玉米淀粉和糯玉米淀粉组成的组。
3．如权利要求2所述的方法，其中所述淀粉的季铵取代度在约0.1-0.4％之间。
4．如权利要求1所述的方法，其中所述阳离子聚合电解质选自由表氯醇-二甲胺缩聚物、表氯醇-二甲胺-乙二胺缩聚物、氯化二烯丙基二甲基铵、聚乙烯亚胺、聚酰胺型胺类、明矾和聚氯化铝组成的组。
5．如权利要求1所述的方法，其中所述高分子量阴离子丙烯酰胺共聚物的分子量大于约10,000,000。
6．如权利要求1所述的方法，其中所述丙烯酰胺共聚物是基本上线性的丙烯酰胺/丙烯酸钠共聚物。
7．如权利要求1所述的方法，其中所述丙烯酰胺共聚物是基本上线性的丙烯酰胺/2-丙烯酰胺-2-甲基丙烷磺酸。
8．如权利要求1所述的方法，其中所述丙烯酰胺共聚物的阴离子电荷的摩尔百分比在约20％至约70％的范围内。
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