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CN110241650A - 一种纸品抄纸着色色浆及其制备方法和应用 - Google Patents

一种纸品抄纸着色色浆及其制备方法和应用 Download PDF

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CN110241650A
CN110241650A CN201910508619.6A CN201910508619A CN110241650A CN 110241650 A CN110241650 A CN 110241650A CN 201910508619 A CN201910508619 A CN 201910508619A CN 110241650 A CN110241650 A CN 110241650A
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颜进华
黄接弟
黄丁源
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Guangdong Youcai New Material Technology Research Co Ltd
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Abstract

本发明公开了一种纸品抄纸着色色浆及其制备方法和应用。(1)将5～30质量份色粉、1～5质量份稳定剂、1～5质量份润湿剂和50‑100质量份水研磨均匀，得到色粉分散液；(2)向色粉分散液中加入2.5～30质量份预聚物并混合均匀，调节pH至1～5，缩合反应2～5小时，得到包覆色粉混合液；(3)将包覆色粉混合液升温至50～80℃，加入1～5质量份阳离子改性剂，滴加入由5～30质量份亲水单体和引发剂组成的混合液，1小时滴完，继续反应1～2小时，冷却至室温，将pH调至8～9，得到纸品抄纸着色色浆。制得的色浆与纤维的亲合性和结合力强，能抵抗抄造水体冲洗和机械力的干扰。

Description

一种纸品抄纸着色色浆及其制备方法和应用
技术领域
本发明属于精细化学品新材料领域，具体涉及一种纸品抄纸着色色浆及其制备方法和应用。
背景技术
色纸是有颜色的纸品，染料能溶于水，与纤维有天然的亲合性，能吸附在纤维表面及内部，着色容易、染色效果明显，因而在抄纸过程中被广泛使用，但染料染色纸品色牢度低，易褪色，不耐久，色纸档次较低。有机颜料比染料的优越之处是有极强的抗日晒牢度，色彩鲜艳持久，是高档色纸青睐的品种。但有机颜料不溶于水，不能与纤维直接结合，应用受到阻碍。
纤维在水中的表面电荷呈负性，与阳离子超细颜料的结合力强，牢度好，染色深度和鲜艳性好，不但可以节约颜料，减少环境污染，提高产品档次，抄纸应用提供了可能。但关于这方面的资料很少。颜料本身是无极性的着色剂，对颜料进行阳离子分散剂包覆，在织物着色有研究报导，发现粒径越小，颜料扩散能力越强，在水中带负电荷的纤维表面越容易通过静电引力吸附颜料。但遗憾的是：颜料用量大于2.5％，染色物的干、湿摩擦牢度和皂洗(褪色和沾色)牢度很低，而且随着颜料用量提高，摩擦牢度更低，说明阳离子分散剂没有紧密反应地包覆在颜料粒子上(周海银，许梅，房宽峻，棉织物浸染用阳离子超细颜料的应用性能，印染，2009，35(2):1-4)。造纸抄造过程采用大量水介质，且经过多次动力传送，可以推测，这种阳离子分散剂对有机颜料包覆牢度将更加不适应于抄纸系统。
发明内容
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种纸品抄纸着色色浆的制备方法。所述方法为用氨基树脂预聚物包覆在色粉颗粒表面从而制得色浆。
本发明的另一目的在于提供上述方法制得的一种纸品抄纸着色色浆。
本发明的再一目的在于提供上述一种纸品抄纸着色色浆在造纸领域中的应用。
本发明目的通过以下技术方案实现：
一种纸品抄纸着色色浆的制备方法，包括以下步骤：
(1)将5～30质量份色粉、1～5质量份稳定剂、1～5质量份润湿剂和50～100质量份水研磨均匀，得到色粉分散液；
(2)向色粉分散液中加入2.5～30质量份氨基树脂预聚物并混合均匀，调节pH至1～5，缩合反应2～5小时，得到包覆色粉混合液；
(3)将包覆色粉混合液升温至50～80℃，加入1～5质量份阳离子改性剂，滴加入由亲水单体和引发剂组成的混合液，1小时滴完，继续反应1～2小时，冷却至室温，将pH调至8～9，得到纸品抄纸着色色浆；
其中亲水单体5～30质量份，引发剂用量占氨基树脂预聚体和亲水单体总质量的0.1～1％。
步骤(1)所述色粉优选为酞菁蓝颜料；更优选为酞菁蓝B。
步骤(1)所述稳定剂优选为大分子亲水性物质；更优选为聚乙烯醇(PVA)、羧甲基纤维素、羧甲基纤维素钠(CMC)、壳聚糖和变性淀粉的一种或两种以上。
所述变性淀粉优选为氧化淀粉、酯化淀粉和醚化淀粉中的一种或两种以上。
步骤(1)所述润湿剂优选为同时具有亲水基团和疏水基团的表面活性剂；更优选为W/O型非离子表面活性剂；最优选为烷基酚聚氧乙烯醚(OP-10)。
步骤(1)所述研磨优选在瓷研磨钵中进行，研磨至得到均匀的色粉分散液。
步骤(2)所述氨基树脂预聚物是指含胺基的三聚氰胺或尿素在碱性条件下与甲醛反应，甲醛将三聚氰胺或尿素分子上的胺基羟甲基化，形成含多个羟甲基的不稳定中间产物，即为氨基树脂预聚物。所述氨基树脂预聚物容易线型交联或体型交联，形成热固性高聚物。
所述氨基树脂预聚物更优选由以下方法制备得到：将三聚氰胺与甲醛按摩尔比1:2～1:6配比混合均匀，调节pH至8～9，在60～80℃反应30分钟，得到透明无色溶液A；将尿素与甲醛按摩尔比1:1.3～1:2配比混合均匀，调节pH至8～9，在60～80℃反应30分钟，得到透明无色溶液B；所述氨基树脂预聚物为透明无色溶液A和B的任意比例混合物，或者为透明无色溶液A，或者为透明无色溶液B。
步骤(2)所述调节pH所用的pH调节剂优选为盐酸、醋酸、甲酸和氯化铵中的一种或两种以上。
步骤(2)所述缩合反应的温度优选为室温。
步骤(3)所述阳离子改性剂优选为聚羟丙基二甲基氯化铵，其由二甲胺与环氧氯丙烷聚合得到。
步骤(3)所述亲水性单体优选为丙烯酸、甲基丙烯酸、亚甲基丁二酸、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酰胺、甲基丙烯酰胺和马来酸酐中的一种或两种以上；更优选为丙烯酰胺和/或丙烯酸。
步骤(3)所述引发剂的用量优选为0.01～0.3质量份；更优选为0.01～0.18质量份。
步骤(3)所述引发剂优选为氧化或氧化-还原体系的自由基引发剂；更优选为过硫酸铵、过硫酸铵/亚硫酸氢钠、过硫酸钾/亚硫酸氢钠、过氧化氢和过硫酸钾中的一种或两种以上。
步骤(3)所述调节pH所用的pH调节剂优选为氢氧化钠、碳酸钠和氨水中的一种或两种以上。
步骤(3)所述纸品抄纸着色色浆可通过加水将其质量浓度调至20～40％；优选为30％。
上述方法制得的一种纸品抄纸着色色浆。
上述一种纸品抄纸着色色浆在造纸领域中的应用。
所述应用优选为在纸品抄纸着色中的应用，具体方法为：色纸成型前浆料中加入纸品抄纸着色色浆和固色剂，混合均匀，抄纸。
所述纸品抄纸着色色浆加入量优选为纸浆质量的1～2％，固色剂加入量优选为0.5～2质量份/100质量份纸浆。纸品抄纸着色色浆的添加量是按其固含量计。
所述固色剂优选为明矾、聚酰胺环氧氯丙烷(PAE)、阳离子聚丙烯酰胺(CPAM)、聚二甲基二烯丙基氯化铵(PDADMAC)和壳聚糖中的一种或两种以上。
所述混合时间优选为大于3min。
本申请所述纸品抄纸着色色浆通过包覆改性技术，用反应型氨基树脂预聚物包覆改性色粉制得，具体是将一定量预聚体和含稳定剂、润湿剂的色浆分散液混合均匀后，在酸性条件下，预聚体在色粉颗粒表面粘附缩聚交联成不溶性大分子，随后通过阳离子改性剂和亲水性单体接枝，使缩聚交联的高分子改性，获得亲水性和阳离子性的改性色浆大分子。
与现有技术相比，本发明具有以下优点及有益效果：
(1)本发明制得的色浆可以用于浆内抄纸着色，与纤维的亲合性和结合力强，能抵抗抄造水体冲洗和机械力的干扰。
(2)本申请通过将氨基树脂预聚物与色粉粘附包裹缩聚改性后，再与阳离子改性剂和亲水单体反应，得到的色浆才具备亲水性并能进行抄纸着色，而未经阳离子改性剂和亲水单体改性的色浆，则会由于亲水性差而粉化，从而无法进行抄纸着色。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例所用色粉均为科莱恩蓝色色粉，C.I.15：3蓝；所用纸浆采用市售漂白浆板，按100克定量抄纸片，抄前浆疏解1分钟；所用阳离子改性剂均为聚羟丙基二甲基氯化铵；所述缩合反应温度均为室温。
实施例1
(1)色粉分散：将色粉5质量份、稳定剂CMC 1质量份、润湿剂(OP-10)1质量份和水50质量份加入到瓷研磨钵中展色研磨一定时间，直至看不到颗粒，得到色粉分散液。
(2)预聚物准备：将三聚氰胺与甲醛按摩尔比1:2配比混合均匀，调节pH至8，在60℃反应30分钟，使之成透明无色溶液，即为预聚物。
(3)包覆色粉：将预聚物2.5质量份(即占色粉质量的50％)加入到色粉分散液中并混合均匀，调节pH至5，缩合2小时。
(4)色浆制备：升温至80℃，向(3)中包覆完成的色粉加入阳离子改性剂1质量份，滴加丙烯酰胺5质量份与过硫酸钾0.1质量份的混合溶液，1小时滴完，继续反应1小时，反应混合物冷却至室温，调节pH至8，得到纸品抄纸着色色浆。加水调整纸品抄纸着色色浆质量浓度至30％，得水性色浆。
(5)抄纸固色：色纸成型前浆料中加入水性色浆(加入量为纸浆质量的1％)和所需固色剂明矾1质量份(对100质量份纸浆)，混合3分钟以上，抄纸。抄纸后，测量色纸颜色，蓝色色密度1.2。废水吸光度0.086。
采用常规FBL蓝色染料染色，相同色粉和固色剂用量下，色纸蓝色密度0.9，废水吸光度0.121。
实施例2
(1)色粉分散：将色粉30质量份、稳定剂PVA5质量份、润湿剂(OP-10)5质量份和水100质量份加入到瓷研磨钵中展色研磨一定时间，直至看不到颗粒，得到色粉分散液。
(2)预聚物准备：将三聚氰胺与甲醛按摩尔比1:6配比混合均匀，调节pH至8，在60℃反应30分钟，使之成透明无色溶液，即为预聚物。
(3)包覆色粉：将预聚物30质量份(即占色粉质量的100％)加入到色粉分散液中并混合均匀，调节pH至1，缩合2小时。
(4)色浆制备：升温至70℃，向(3)中包覆完成的色粉加入阳离子改性剂5质量份，滴加亲水单体丙烯酰胺20质量份与过硫酸铵0.3质量份的混合溶液，1小时滴完，继续反应2小时，反应混合物冷却至室温，调节pH至9，得到纸品抄纸着色色浆。加水调整纸品抄纸着色色浆质量浓度至30％，得水性色浆。
(5)抄纸固色：色纸成型前浆料中加入水性色浆(加入量为纸浆质量的1％)和所需固色剂湿强剂聚酰胺环氧氯丙烷1质量份(对100质量份纸浆)，混合3分钟以上，抄纸。抄纸后，测量色纸颜色，蓝色色密度1.2。废水吸光度0.086。
采用常规FBL蓝色染料染色，相同色粉和固色剂用量下，色纸蓝色密度0.9，废水吸光度0.121。
实施例3
(1)色粉分散：将色粉15质量份、稳定剂CMC 3质量份、润湿剂(OP-10)2质量份和水80质量份加入到瓷研磨钵中展色研磨一定时间，直至看不到颗粒，得到色粉分散液。
(2)预聚物准备：将尿素与甲醛按摩尔比1:2配比混合均匀，调节pH至8，在60℃反应30分钟，使之成透明无色溶液，即为预聚物。
(3)包覆色粉：将预聚物7.5质量份(即占色粉质量的50％)加入到色粉分散液中并混合均匀，调节pH至5，缩合5小时。
(4)色浆制备：升温至80℃，向(3)中包覆完成的色粉加入阳离子改性剂3质量份，滴加亲水单体丙烯酸10质量份与过硫酸铵0.2质量份的混合溶液，1小时滴完，继续反应2小时，反应混合物冷却至室温，调pH至8，得到纸品抄纸着色色浆。加水调整纸品抄纸着色色浆质量浓度至30％，得水性色浆。
(5)抄纸固色：色纸成型前浆料中加入水性色浆(加入量为纸浆质量的1％)和所需固色剂聚二甲基二烯丙基氯化铵(PDADMAC)2质量份(对100质量份纸浆)，混合3分钟以上，抄纸。抄纸后，测量色纸颜色，蓝色色密度1.12。废水吸光度0.095。
采用常规FBL蓝色染料染色，相同色粉和固色剂用量下，色纸蓝色密度0.9，废水吸光度0.121。
实施例4
(1)色粉分散：将色粉15质量份、稳定剂PVA 3质量份、润湿剂(OP-10)3质量份和水80质量份加入到瓷研磨钵中展色研磨一定时间，直至直至看不到颗粒，得到色粉分散液。
(2)预聚物准备：将尿素与甲醛按摩尔比1:2配比混合均匀，调节pH至9，在60℃反应30分钟，使之成透明无色溶液A；将三聚氰胺与甲醛按摩尔比1:3配比加入，调节pH至9，在60℃反应30分钟，使之成透明无色溶液B；将A与B按1:1质量比混合，即得预聚体。
(3)包覆色粉：将预聚物22.5质量份(即占色粉质量的150％)加入到色粉分散液中并混合均匀，调节pH至5，缩合5小时。
(4)色浆制备：升温至80℃，向(3)中包覆完成的色粉加入阳离子改性剂4质量份，滴加亲水单体丙烯酰胺30质量份与过硫酸钾0.3质量份的混合溶液，1小时滴完，继续反应2小时，反应混合物冷却至室温，调节pH至9，得到纸品抄纸着色色浆。加水调整纸品抄纸着色色浆质量浓度至30％，得水性色浆。
(5)抄纸固色：色纸成型前浆料中加入水性色浆(加入量为纸浆质量的1％)和所需固色剂聚二甲基二烯丙基氯化铵(PDADMAC)2质量份(对100质量份纸浆)，混合3分钟以上，抄纸。抄纸后，测量色纸颜色，蓝色色密度1.12。废水吸光度0.095。
采用常规FBL蓝色染料染色，相同色粉和固色剂用量下，色纸蓝色密度0.9，废水吸光度0.121。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种纸品抄纸着色色浆的制备方法，其特征在于，包括以下步骤：
(1)将5～30质量份色粉、1～5质量份稳定剂、1～5质量份润湿剂和50～100质量份水研磨均匀，得到色粉分散液；
(2)向色粉分散液中加入2.5～30质量份氨基树脂预聚物并混合均匀，调节pH至1～5，缩合反应2～5小时，得到包覆色粉混合液；
(3)将包覆色粉混合液升温至50～80℃，加入1～5质量份阳离子改性剂，滴加入由亲水单体和引发剂组成的混合液，1小时滴完，继续反应1～2小时，冷却至室温，将pH调至8～9，得到纸品抄纸着色色浆；
其中亲水单体5～30质量份，引发剂用量占氨基树脂预聚体和亲水单体总质量的0.1～1％。
2.根据权利要求1所述一种纸品抄纸着色色浆的制备方法，其特征在于，步骤(2)所述氨基树脂预聚物是指含胺基的三聚氰胺或尿素在碱性条件下与甲醛反应，甲醛将三聚氰胺或尿素分子上的胺基羟甲基化，形成含多个羟甲基的不稳定中间产物，即为氨基树脂预聚物。
3.根据权利要求2所述一种纸品抄纸着色色浆的制备方法，其特征在于，所述氨基树脂预聚物由以下方法制备得到：将三聚氰胺与甲醛按摩尔比1:2～1:6配比混合均匀，调节pH至8～9，在60～80℃反应30分钟，得到透明无色溶液A；将尿素与甲醛按摩尔比1:1.3～1:2配比混合均匀，调节pH至8～9，在60～80℃反应30分钟，得到透明无色溶液B；所述氨基树脂预聚物为透明无色溶液A和B的任意比例混合物，或者为透明无色溶液A，或者为透明无色溶液B。
4.根据权利要求1或2或3所述一种纸品抄纸着色色浆的制备方法，其特征在于，步骤(1)所述稳定剂为大分子亲水性物质；
所述润湿剂为同时具有亲水基团和疏水基团的表面活性剂；
步骤(3)所述亲水性单体为丙烯酸、甲基丙烯酸、亚甲基丁二酸、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酰胺、甲基丙烯酰胺和马来酸酐中的一种或两种以上；所述阳离子改性剂为聚羟丙基二甲基氯化铵；
所述引发剂为氧化或氧化-还原体系的自由基引发剂。
5.根据权利要求4所述一种纸品抄纸着色色浆的制备方法，其特征在于，步骤(1)所述稳定剂为聚乙烯醇、羧甲基纤维素、羧甲基纤维素钠、壳聚糖和变性淀粉的一种或两种以上；所述变性淀粉为氧化淀粉、酯化淀粉和醚化淀粉中的一种或两种以上；
所述润湿剂为W/O型非离子表面活性剂；
步骤(3)所述引发剂为过硫酸铵、过硫酸铵/亚硫酸氢钠、过硫酸钾/亚硫酸氢钠、过氧化氢和过硫酸钾中的一种或两种以上；所述引发剂的用量为0.01～0.3质量份。
6.根据权利要求4所述一种纸品抄纸着色色浆的制备方法，其特征在于，
步骤(1)所述色粉为酞菁蓝颜料；
步骤(2)所述缩合反应的温度为室温；所述调节pH所用的pH调节剂为盐酸、醋酸、甲酸和氯化铵中的一种或两种以上；
步骤(3)所述调节pH所用的pH调节剂为氢氧化钠、碳酸钠和氨水中的一种或两种以上。
7.权利要求1～6任一项所述方法制得的一种纸品抄纸着色色浆。
8.权利要求7任一项所述一种纸品抄纸着色色浆在造纸领域中的应用。
9.根据权利要求8所述一种纸品抄纸着色色浆在造纸领域中的应用，其特征在于，在纸品抄纸着色中的应用，具体方法为：色纸成型前浆料中加入纸品抄纸着色色浆和固色剂，混合均匀，抄纸。
10.根据权利要求9所述一种纸品抄纸着色色浆在造纸领域中的应用，其特征在于，所述纸品抄纸着色色浆加入量为纸浆质量的1～2％，固色剂加入量为0.5～2质量份/100质量份纸浆；
所述固色剂为明矾、聚酰胺环氧氯丙烷、阳离子聚丙烯酰胺、聚二甲基二烯丙基氯化铵和壳聚糖中的一种或两种以上；所述混合时间为大于3min。
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