CN111608014B - 一种高性能低定量字典纸及其制备方法 - Google Patents

一种高性能低定量字典纸及其制备方法 Download PDF

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CN111608014B
CN111608014B CN202010286035.1A CN202010286035A CN111608014B CN 111608014 B CN111608014 B CN 111608014B CN 202010286035 A CN202010286035 A CN 202010286035A CN 111608014 B CN111608014 B CN 111608014B
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pulp
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coating
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CN111608014A (zh
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王敏良
戴贤中
赵建华
毛学米
杨昌余
江利
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Xianhe Co ltd
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Abstract

本发明公开了一种高性能低定量字典纸及其制备方法，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量22~30g/m2，制备植物纤维层的浆料包括质量分数为45~65%的漂白本色针叶木浆及35%~55%的漂白阔叶木浆，制备涂层的涂料以重量份记，原料包括：200~300份改性填料，40~60份助留剂，1~2份保水剂，1~3份润滑剂，0.05~0.1份消泡剂，5~10份氢氧化钠以及500~1000份水。本发明在植物纤维层两侧的涂层中使用改性填料，改性填料表面引入的物质可以与纤维发生反应从而使将填料与纤维层牢固连接，提高填料的留着率；并且可以通过吸附油墨中的呈色物质防止透页和脱墨现象发生。

Description

一种高性能低定量字典纸及其制备方法
技术领域
本发明涉及造纸技术领域，尤其是涉及一种高性能低定量字典纸及其制备方法。
背景技术
字典纸是一种高级印刷用纸，其特点是要求较高的不透明度、平滑度和耐久性，纸面需洁白细腻、强韧耐折。一般通过在字典纸制备过程中添加碳酸钙等填料来提高字典纸的不透明度、白度和吸油墨性，例如，在中国专利文献上公开的“一种涂布字典纸的生产方法”，其公告号CN102839559B，采用双面涂布法制备字典纸，涂料的配方包括：80份重质超细碳酸钙，20份金红石型钛白粉，10～15份丁苯乳胶，15～20份季胺型阳离子淀粉，0.3～0.5份保水剂，0.01～0.03份分散剂，0.5～0.7份润滑剂，0.01～0.03消泡剂。该专利通过在植物纤维层两面涂布具有填料的涂层，提高纸页的平滑性，并且因为两侧的涂层与中间层具有不同的折光率，增大了纸页的不透明度。
但是现有的造纸技术中，主要通过阳离子淀粉等助留剂与纤维结合形成絮凝物不能通过的网，从而将填料与细小纤维截留在纸页中来提高填料的留着率，由于填料与纤维在表面极性、表面化学组成、表面能等表面性质存在着较大不同，二者之间并无结合力，所以填料很容易在外力作用下脱离絮凝物而流失，填料留着率不高，影响纸张性能，增大填料用量又会导致后期印刷过程中出现掉粉现象。并且填料粒径小，易团聚，影响其光散射性能和纸张的均匀度。
发明内容
本发明是为了克服现有的字典纸制备过程中，由于填料与纤维之间并无结合力，所以很容易在外力作用下脱离絮凝物而流失，填料留着率不高，影响纸张性能；并且填料粒径小，易团聚，影响其光散射性能和纸张的均匀度的问题，提供一种高性能低定量字典纸及其制备方法，对填料进行表面改性，提高了填料的分散性，并通过改性后的填料与纤维之间的反应使填料与纤维通过化学作用连接，提高填料留着率，从而提高纸张使用性能。
为了实现上述目的，本发明采用以下技术方案：
一种高性能低定量字典纸，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量22～30g/m2，制备所述植物纤维层的浆料包括质量分数为45～65％的漂白本色针叶木浆及35％～55％的漂白阔叶木浆，制备所述涂层的涂料以重量份记，原料包括：200～300份改性填料，40～60份助留剂，1～2份保水剂，1～3份润滑剂，0.05～0.1份消泡剂，5～10份氢氧化钠以及500～1000份水。
作为优选，涂料中所述的改性填料包括改性轻质碳酸钙和改性钛白粉的一种或两种，其制备方法为：
A)将轻质碳酸钙或钛白粉分散在二甲苯中，加入γ-氯丙基三甲氧基硅烷，75～85℃加热反应8～10h后过滤，将产物在甲苯中抽提20～30h，得到氯丙基化填料；所述轻质碳酸钙或钛白粉与γ-氯丙基三甲氧基硅烷的质量体积比为1g：(1～2mL)；
B)将氯丙基化填料加入聚环氧氯丙烷-二甲胺溶液和NaOH的混合溶液中，85～95℃下搅拌反应3～5h，所述混合溶液中聚环氧氯丙烷-二甲胺的质量分数为10～15％，氢氧化钠的质量分数为4～6％，加入的氯丙基化填料与混合溶液的质量体积比为1g：(20～30mL)；
C)向步骤B)反应后的溶液中加入与聚环氧氯丙烷-二甲胺质量比为1:(1～3)的聚乙烯亚胺，85～95℃下继续搅拌反应3～5h后过滤，将产物用甲醇和水洗涤并烘干后，得到所述改性填料。
现有技术中的字典纸当纸张定量小于30g/m2时，随着定量降低，纸的厚度降低，纸页的不透明度和紧度也随之下降，导致字典印刷后透页现象的产生，影响阅读，并且纸页易烂；而定量增加，又会加重字典质量，不方便携带。本发明中的字典纸在植物纤维层两侧设置包含改性填料的涂层，由于改性填料对光有良好的散射作用，三层的折光率不同，使纸页具有良好的不透明度，避免印刷后产生透印现象；改性填料不直接加入植物纤维层内，提高了纤维内部的结合力，使纸面紧度提高，提高纸页强度，字典反复翻阅不易烂；并且通过涂层的涂布和压光处理，可以提高纸页的平滑度，减小纸页间的摩擦，便于字典翻阅；因此在降低了纸页定量的同时使纸页依旧具有良好的使用性能。
为了使涂层中的填料与植物纤维层更好的结合，增大涂料的留着率，以保证纸页的不透明度，本发明对填料进行了表面改性，先通过步骤A)，利用硅烷偶联剂γ-氯丙基三甲氧基硅烷与碳酸钙或钛白粉上的羟基反应，在填料表面引入氯丙基；然后经过步骤B)，通过氯丙基与聚环氧氯丙烷-二甲胺上的胺基反应，将聚环氧氯丙烷-二甲胺接枝在填料表面；再通过步骤C)，利用聚环氧氯丙烷-二甲胺上的端基氯与聚乙烯亚胺中的胺发生取代反应，再将聚乙烯亚胺引入填料表面，得到表面经聚环氧氯丙烷-二甲胺和聚乙烯亚胺接枝物改性的改性填料。填料经大分子聚合物表面改性后，表面能降低，比外加分散剂时具有更好的分散性和分散稳定性，加入涂料中及涂布在植物纤维层上后不会发生团聚，提高了纸页的不透明度和平滑度。
并且改性填料涂布在植物纤维层上后，在碱性条件下填料表面接枝的聚环氧氯丙烷-二甲胺中的氯甲基可以和纤维素的离子发生亲核反应，同时聚合物末端基也能转变为环氧基，然后和纤维素表面的羟基反应与纤维素分子连接，从而通过聚环氧氯丙烷-二甲胺层将填料与植物纤维层通过化学键连接起来，与吸附助留作用相比，大大提供了填料与植物纤维层之间的连接牢固性，有效提高了填料的留着率，进一步提高了纸页的不透明度。同时填料与纤维之间的聚环氧氯丙烷-二甲胺层也具有良好的絮凝助留效果，有利于细小纤维等细小组分的留着，避免纸张出现掉毛掉粉现象。
为了避免低定量纸印刷后发生透页现象，本发明还在接枝在改性填料表面的聚环氧氯丙烷-二甲胺上引入了聚乙烯亚胺，随着聚环氧氯丙烷-二甲胺与纤维的反应，聚乙烯亚胺同时被固定在纤维层和填料之间。由于聚乙烯亚胺带有正电荷，而印刷过程中使用的油墨中的呈色物质大都含有阴离子基团，带负电，因此印刷过程中油墨喷射到涂层上后，涂层中的聚乙烯亚胺可以通过吸附作用加速纸张对油墨的吸收，从而加速油墨的干燥，避免双面印刷时脱墨现象的发生。同时，油墨中带负电的呈色物质被聚乙烯亚胺吸附后，可以将呈色物质固定在涂层内，不会渗透到植物纤维层及背面，避免了印刷后透页现象的发生。因此本发明中制备出的低定量字典纸制备过程中填料的留着率高，不透明度、平滑度和紧度好，印刷过程中不易产生脱墨和透页现象，字典的使用性能佳。
作为优选，涂料中所述的助留剂为阳离子淀粉、丁苯胶乳和聚乙烯醇中的一种或多种。
作为优选，涂料中所述的保水剂为羧甲基纤维素钠或壳聚糖。
作为优选，涂料中所述的润滑剂为硬脂酸钙。
作为优选，涂料中所述的消泡剂为聚醚型消泡剂或有机硅消泡剂。
作为优选，植物纤维层的浆料浆度为65～73oSR，湿重2.0～3.0g，pH为7.5～8.5，所述浆料中添加吨纸用量为0.5～1.0kg的脱气剂，5～8kg的浆内胶以及3～10kg的AKD。
作为优选，所述浆内胶为阳离子淀粉，所述AKD为烷基烯酮二聚体。
本发明还公开了一种上述高性能低定量字典纸的制备方法，包括如下步骤：
(1)制备磨浆后配浆得到植物纤维层的浆料，并向浆料中加入AKD、浆内胶以及脱气剂；
(2)浆料进行上网抄造得到纸页；
(3)对纸页进行压榨和前干燥；
(4)用涂料对纸页进行双面涂布，双面的涂布量均为3～4g/m2；
(5)涂布后的纸页先进入非接触的热风干燥箱预干燥，再进入后干燥部最终干燥；
(6)干燥后的纸页进行压光后得到所述高性能低定量字典纸。
作为优选，步骤(2)中抄造时上网浓度为0.5～0.6％，车速为500～600m/min；步骤(3)中前干燥后的纸页水分为10～15％；步骤(5)中最终干燥后的纸页水分为3～5％。
因此，本发明具有如下有益效果：
(1)在植物纤维层两侧设置包含改性填料的涂层，提高了纸页的不透明度、紧度和平滑度，使字典纸在低定量情况下也具有良好的使用性能；
(2)通过聚环氧氯丙烷-二甲胺和聚乙烯亚胺对填料进行改性，改善填料的分散性，并且使填料可以通过聚环氧氯丙烷-二甲胺与纤维层通过化学键牢固连接，大大提高填料的留着率，从而提高纸页的不透明度和平滑度，避免印刷过程中掉粉现象的发生；
(3)填料表面引入的聚乙烯亚胺在印刷过程中可以吸附油墨中的呈色物质，从而加速了油墨的吸收和干燥，避免脱墨现象产生；同时可以将呈色物质固定在涂层内，不会渗透到植物纤维层及背面，避免透页现象的发生。
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。本发明实施例中使用的原料若非特指均为市售或本领域常用原料。
实施例1：
一种高性能低定量字典纸，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量25.71g/m2，制备植物纤维层的浆料包括质量分数为55％的漂白本色针叶木浆及45％的漂白阔叶木浆，浆度为69oSR，湿重2.5g，pH为8，浆料中添加吨纸用量为0.8kg的市售脱气剂，6kg的阳离子淀粉以及8kg的烷基烯酮二聚体。制备涂层的涂料以重量份记，原料包括：250份改性填料，50份阳离子淀粉，1.5份羧甲基纤维素钠，2份硬脂酸钙，0.08份聚醚型消泡剂，8份氢氧化钠以及800份水。
改性填料包括230份改性轻质碳酸钙和20份改性钛白粉，其制备方法为：
A)将轻质碳酸钙或钛白粉分散在二甲苯中，加入γ-氯丙基三甲氧基硅烷，80℃加热反应9h后过滤，将产物在甲苯中抽提24h，得到氯丙基化填料；轻质碳酸钙或钛白粉与γ-氯丙基三甲氧基硅烷的质量体积比为1g：1.5mL；
B)将氯丙基化填料加入聚环氧氯丙烷-二甲胺溶液和NaOH的混合溶液中，90℃下搅拌反应4h，混合溶液中聚环氧氯丙烷-二甲胺的质量分数为12％，氢氧化钠的质量分数为5％，加入的氯丙基化填料与混合溶液的质量体积比为1g：25mL；
C)向步骤B)反应后的溶液中加入与聚环氧氯丙烷-二甲胺质量比为1:2的聚乙烯亚胺，90℃下继续搅拌反应4h后过滤，将产物用甲醇和水洗涤并烘干后，得到改性填料。
上述高性能低定量字典纸的制备方法为：
(1)制备磨浆后配浆得到植物纤维层的浆料，并向浆料中加入烷基烯酮二聚体、阳离子淀粉以及脱气剂；
(2)浆料进行上网抄造得到纸页，上网浓度为0.5％，车速为550m/min；
(3)对纸页进行压榨和前干燥，压榨部由四辊三压区组成，三道压区的压力分别是：60kN/m2、80kN/m2、120kN/m2，出压榨后的湿纸页的干度为42％，前干燥后的纸页水分为12％；
(4)用涂料对纸页进行双面涂布，双面的涂布量均为4.16g/m2；
(5)涂布后的纸页先进入非接触的热风干燥箱预干燥，再进入后干燥部最终干燥，最终干燥后的纸页水分为4％；
(6)干燥后的纸页进入双压区软压光表面整饰后得到高性能低定量字典纸，双压区软压光的压力为160kN/m2，热辊表面温度为150℃。
实施例2：
一种高性能低定量字典纸，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量22.33g/m2，制备植物纤维层的浆料包括质量分数为45％的漂白本色针叶木浆及55％的漂白阔叶木浆，浆度为65oSR，湿重2.0g，pH为7.5，浆料中添加吨纸用量为0.5kg的市售脱气剂，5kg的阳离子淀粉以及3kg的烷基烯酮二聚体。制备涂层的涂料以重量份记，原料包括：200份改性填料，40份阳离子淀粉，1份羧甲基纤维素钠，1份硬脂酸钙，0.05份聚醚型消泡剂，5份氢氧化钠以及500份水。
改性填料包括200份改性轻质碳酸钙，其制备方法为：
A)将轻质碳酸钙分散在二甲苯中，加入γ-氯丙基三甲氧基硅烷，75℃加热反应8h后过滤，将产物在甲苯中抽提20h，得到氯丙基化填料；轻质碳酸钙或钛白粉与γ-氯丙基三甲氧基硅烷的质量体积比为1g：1mL；
B)将氯丙基化填料加入聚环氧氯丙烷-二甲胺溶液和NaOH的混合溶液中，85℃下搅拌反应3h，混合溶液中聚环氧氯丙烷-二甲胺的质量分数为10％，氢氧化钠的质量分数为4％，加入的氯丙基化填料与混合溶液的质量体积比为1g：20mL；
C)向步骤B)反应后的溶液中加入与聚环氧氯丙烷-二甲胺质量比为1:1的聚乙烯亚胺，85℃下继续搅拌反应3h后过滤，将产物用甲醇和水洗涤并烘干后，得到改性填料。
上述高性能低定量字典纸的制备方法为：
(1)制备磨浆后配浆得到植物纤维层的浆料，并向浆料中加入烷基烯酮二聚体、阳离子淀粉以及脱气剂；
(2)浆料进行上网抄造得到纸页，上网浓度为0.5％，车速为500m/min；
(3)对纸页进行压榨和前干燥，压榨部由四辊三压区组成，三道压区的压力分别是：60kN/m2、80kN/m2、120kN/m2，出压榨后的湿纸页的干度为40％，前干燥后的纸页水分为10％；
(4)用涂料对纸页进行双面涂布，双面的涂布量均为4.92g/m2；
(5)涂布后的纸页先进入非接触的热风干燥箱预干燥，再进入后干燥部最终干燥，最终干燥后的纸页水分为3％；
(6)干燥后的纸页进入双压区软压光表面整饰后得到高性能低定量字典纸，双压区软压光的压力为160kN/m2，热辊表面温度为150℃。
实施例3：
一种高性能低定量字典纸，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量29.75g/m2，制备植物纤维层的浆料包括质量分数为65％的漂白本色针叶木浆及35％的漂白阔叶木浆，浆度为73oSR，湿重3.0g，pH为8.5，浆料中添加吨纸用量为1.0kg的市售脱气剂，8kg的阳离子淀粉以及10kg的烷基烯酮二聚体。制备涂层的涂料以重量份记，原料包括：300份改性填料，50份阳离子淀粉，10份丁苯乳胶，2份羧甲基纤维素钠，3份硬脂酸钙，0.1份
聚醚型消泡剂，10份氢氧化钠以及1000份水。
改性填料包括250份改性轻质碳酸钙和50份改性钛白粉，其制备方法为：
A)将轻质碳酸钙分散在二甲苯中，加入γ-氯丙基三甲氧基硅烷，85℃加热反应10h后过滤，将产物在甲苯中抽提30h，得到氯丙基化填料；轻质碳酸钙或钛白粉与γ-氯丙基三甲氧基硅烷的质量体积比为1g：2mL；
B)将氯丙基化填料加入聚环氧氯丙烷-二甲胺溶液和NaOH的混合溶液中，95℃下搅拌反应5h，混合溶液中聚环氧氯丙烷-二甲胺的质量分数为15％，氢氧化钠的质量分数为6％，加入的氯丙基化填料与混合溶液的质量体积比为1g：30mL；
C)向步骤B)反应后的溶液中加入与聚环氧氯丙烷-二甲胺质量比为1:3的聚乙烯亚胺，95℃下继续搅拌反应5h后过滤，将产物用甲醇和水洗涤并烘干后，得到改性填料。
上述高性能低定量字典纸的制备方法为：
(1)制备磨浆后配浆得到植物纤维层的浆料，并向浆料中加入烷基烯酮二聚体、阳离子淀粉以及脱气剂；
(2)浆料进行上网抄造得到纸页，上网浓度为0.6％，车速为600m/min；
(3)对纸页进行压榨和前干燥，压榨部由四辊三压区组成，三道压区的压力分别是：60kN/m2、80kN/m2、120kN/m2，出压榨后的湿纸页的干度为43％，前干燥后的纸页水分为15％；
(4)用涂料对纸页进行双面涂布，双面的涂布量均为3.18g/m2；
(5)涂布后的纸页先进入非接触的热风干燥箱预干燥，再进入后干燥部最终干燥，最终干燥后的纸页水分为5％；
(6)干燥后的纸页进入双压区软压光表面整饰后得到高性能低定量字典纸，双压区软压光的压力为160kN/m2，热辊表面温度为150℃。
对比例1：
对比例1与实施例1的区别在于，对比例1的涂料中填料使用不经改性的轻质碳酸钙和钛白粉，其余均与实施例1中相同。
对上述实施例中制备的字典纸性能进行测试，结果如表1所示。
表1：字典纸性能测试结果。
编号 不透明度(％) 平滑度(s) 紧度(g/cm<sup>3</sup>) 是否有透页现象 是否有脱墨现象
实施例1 85.1 178 0.828 否 否
实施例2 82.5 162 0.821 否 否
实施例3 87.2 192 0.833 否 否
对比例1 79.1 160 0.825 是 是
从表1中可以看出，实施例1～3中采用本发明中的原料和方法制备出的字典纸定量低且各项性能良好，印刷过程中无脱墨和透页现象产生。而对比例1中不使用本发明中的方法对填料进行改性，制得的字典纸的不透明度和平滑度均比实施例1中有所下降，并且印刷过程中会有透页和脱墨现象发生，影响字典的印刷性能。

Claims (9)

1.一种高性能低定量字典纸，其特征是，包括植物纤维层和设置在植物纤维层两侧的涂层，纸张定量22~30g/m2，制备所述植物纤维层的浆料包括质量分数为45~65%的漂白本色针叶木浆及35%~55%的漂白阔叶木浆，制备所述涂层的涂料以重量份记，原料包括：200~300份改性填料，40~60份助留剂，1~2份保水剂，1~3份润滑剂，0.05~0.1份消泡剂，5~10份氢氧化钠以及500~1000份水；
所述的改性填料包括改性轻质碳酸钙和改性钛白粉的一种或两种，其制备方法为：
A）将轻质碳酸钙或钛白粉分散在二甲苯中，加入γ-氯丙基三甲氧基硅烷，75~85℃加热反应8~10h后过滤，将产物在甲苯中抽提20~30h，得到氯丙基化填料；所述轻质碳酸钙或钛白粉与γ-氯丙基三甲氧基硅烷的质量体积比为1g：（1~2mL）；
B）将氯丙基化填料加入聚环氧氯丙烷-二甲胺溶液和NaOH的混合溶液中，85~95℃下搅拌反应3~5h，所述混合溶液中聚环氧氯丙烷-二甲胺的质量分数为10~15%，氢氧化钠的质量分数为4~6%，加入的氯丙基化填料与混合溶液的质量体积比为1g：（20~30mL）；
C）向步骤B）反应后的溶液中加入与聚环氧氯丙烷-二甲胺质量比为1:（1~3）的聚乙烯亚胺，85~95℃下继续搅拌反应3~5h后过滤，将产物用甲醇和水洗涤并烘干后，得到所述改性填料。
2.根据权利要求1所述的一种高性能低定量字典纸，其特征是，涂料中所述的助留剂为阳离子淀粉、丁苯胶乳和聚乙烯醇中的一种或多种。
3.根据权利要求1所述的一种高性能低定量字典纸，其特征是，涂料中所述的保水剂为羧甲基纤维素钠或壳聚糖。
4.根据权利要求1所述的一种高性能低定量字典纸，其特征是，涂料中所述的润滑剂为硬脂酸钙。
5.根据权利要求1所述的一种高性能低定量字典纸，其特征是，涂料中所述的消泡剂为聚醚型消泡剂或有机硅消泡剂。
6.根据权利要求1所述的一种高性能低定量字典纸，其特征是，植物纤维层的浆料浆度为65~73oSR，湿重2.0~3.0g，pH为7.5~8.5，所述浆料中添加吨纸用量为0.5~1.0kg的脱气剂，5~8kg的浆内胶以及3~10kg的AKD。
7.根据权利要求6所述的一种高性能低定量字典纸，其特征是，所述浆内胶为阳离子淀粉，所述AKD为烷基烯酮二聚体。
8.一种如权利要求1~7任一所述的高性能低定量字典纸的制备方法，其特征是，包括如下步骤：
（1）制备磨浆后配浆得到植物纤维层的浆料，并向浆料中加入AKD、浆内胶以及脱气剂；
（2）浆料进行上网抄造得到纸页；
（3）对纸页进行压榨和前干燥；
（4）用涂料对纸页进行双面涂布，双面的涂布量均为3~5g/m2；
（5）涂布后的纸页先进入非接触的热风干燥箱预干燥，再进入后干燥部最终干燥；
（6）干燥后的纸页进行压光后得到所述高性能低定量字典纸。
9.根据权利要求8所述的一种高性能低定量字典纸的制备方法，其特征是，步骤（2）中抄造时上网浓度为0.5~0.6%，车速为500~600m/min；步骤（3）中前干燥后的纸页水分为10~15%；步骤（5）中最终干燥后的纸页水分为3~5%。
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