CN101999020A - 改良的荧光增白组合物 - Google Patents

改良的荧光增白组合物 Download PDF

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CN101999020A
CN101999020A CN200980110072.9A CN200980110072A CN101999020A CN 101999020 A CN101999020 A CN 101999020A CN 200980110072 A CN200980110072 A CN 200980110072A CN 101999020 A CN101999020 A CN 101999020A
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A·C·杰克逊
D·普蒂帕特
C·克莱因
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Abstract

用于纸张的施胶组合物，其特征在于，所述施胶组合物含有(a)至少一种式(1)的荧光增白剂，(b)镁盐，以及(c)粘合剂，其选自原淀粉、酶改性的淀粉和化学改性的淀粉；对于每份组分(a)存在0.1至15份的组分(b)。

Description

改良的荧光增白组合物
本发明涉及在施胶机上施加到纸面上时提供优异的荧光增白作用的组合物。
背景技术
对于纸制品的最终用户而言，高水平的白度是重要的参数。造纸业最重要的原材料是纤维素、纸浆和木质素，它们天然地吸收蓝色光并因此呈微黄色且赋予纸张的灰暗的外观。在造纸业中使用荧光增白剂通过吸收具有350-360nm的最大波长的紫外光并将其转化为具有440nm的最大波长的可见蓝光来补偿蓝光的吸收。
在纸张的生产中，可以在造纸机的湿部或在纸的表面或在这两个位置添加荧光增白剂。通常，不可能通过单独地在湿部添加来获得高品质纸张所需的白度水平。
将荧光增白剂添加到纸张表面的一般方法是，在施胶压机上与施胶剂一同施加荧光增白剂的水溶液，所述施胶剂典型地是原淀粉或者酶或化学改性的淀粉。使预成型的纸张片材通过双辊钳口，进入钳口充满施胶溶液。纸张吸收溶液的一部分，剩余部分在钳口中被移除。
除淀粉和荧光增白剂之外，施胶溶液可以含有其他旨在提供特定性能的化学制剂。这些化学制剂包括消泡剂、蜡乳液、染料、颜料和无机盐。
为达到更高的白度水平，向新型荧光增白剂的研发投入了相当大的努力。参见，例如日本公开62-106965、PCT申请WO 98/42685、US专利5,873,913以及欧洲专利1,763,519。
GB 1239818公开了衍生自三嗪基氨基茋的六磺酸盐化的荧光增白剂。实施例1至6公开了它们的钠盐。仅在用于六磺酸盐化的荧光增白剂的一系列可能的反离子中提到了镁，同样仅在一系列可能的粘合剂中作为表面施胶组合物中的成分提到了淀粉。
仍然存在对于在纸张中实现高白度水平的更有效手段的需求。
发明描述
出人意料地，我们发现当在淀粉施胶组合物中与镁盐结合地施加到纸张表面时，式(1)的荧光增白剂带来增强的增白效果。如果没有另外注明，下文中的“份”是指重量份。
本发明因此提供一种在施胶压机中增白纸张的方法，其特征在于施胶组合物中含有
(a)至少一种式(1)的荧光增白剂
Figure BPA00001229579400021
其中，
R1是氢或SO3M，
R2是氢或SO3M，
R3是氢、C1-4烷基、C2-3羟基烷基、CH2CO2M、CH2CH2CONH2或CH2CH2CN，
R4是C1-4烷基、C2-3羟基烷基、CH2CO2M、CH(CO2M)CH2CO2M或CH(CO2M)CH2CH2CO2M、苄基，或者
R3和R4与相邻的氮原子一起表示吗啉环，并且
M是氢、碱金属阳离子、铵、单甲基-二-C2-C3羟基烷基铵、二甲基-单-C2-C3-羟基烷基铵、被C2-C3羟基烷基单-、二-或三取代的铵，或所述化合物的混合物，
(b)镁盐；以及
(c)粘合剂，其选自原淀粉、酶改性的淀粉和化学改性的淀粉。
对于每份组分(a)存在0.1至15份组分(b)。
优选的式(1)化合物是其中R3代表氢、甲基、乙基、正丙基、异丙基、β-羟乙基、β-羟丙基、CH2CO2M、CH2CH2CONH2或CH2CH2CN，并且R4代表甲基、乙基、正丙基、异丙基、2-丁基、β-羟乙基、β-羟丙基、CH2CO2M、CH(CO2M)CH2CO2M、CH(CO2M)CH2CH2CO2M或苄基的那些。
式(2)和(3)的荧光增白剂是式(1)的荧光增白剂的特定实例，但本发明不限于这两种特定实例。
Figure BPA00001229579400031
镁盐可以是，例如，乙酸镁、溴化镁、氯化镁、甲酸镁、碘化镁、硝酸镁、硫酸镁或硫代硫酸镁。优选地，镁盐是氯化镁、硫酸镁或硫代硫酸镁。最优选地，镁盐是氯化镁。
优选地，对于每份组分(a)存在0.15至10份的组分(b)。
最优选地，对于每份组分(a)存在0.4至5份的组分(b)。
为了在施胶压机中处理纸张，可以使用含有0.2至30，优选1至15克每升荧光增白剂的施胶组合物。基于施胶组合物的总重计，施胶组合物还含有优选浓度为2至15重量％的粘合剂。pH典型地处于5-9，优选6-8的范围内。
粘合剂或胶选自原淀粉、酶改性淀粉和化学改性淀粉。改性淀粉优选为氧化的淀粉、羟乙基化淀粉、乙酰化淀粉。原淀粉优选为阴离子淀粉、阳离子淀粉或两性淀粉。虽然淀粉源可以是任意的，淀粉源优选为谷物、小麦、马铃薯、大米、木薯或西米。可以存在一种或多种第二粘合剂，优选聚乙烯醇或羧甲基纤维素。
本发明的另外的主题是纸的荧光增白方法，包括以下步骤
a)将施胶组合物施加到纸上，
b)干燥处理过的纸。
优选地，将消泡剂、蜡乳液、染料和/或颜料添加到所述施胶组合物中。
下列实施例应当更详细地解释本发明。如果没有另外说明，“％”和“份”是指按重量计。
实施例1
通过如下方式制备施胶组合物：在60℃下以这样的量将式(2)的荧光增白剂添加到搅拌的氯化镁(最终浓度为8g/l)和阴离子型氧化马铃薯淀粉(购自AVEBE B.A.的Perfectamyl A4692)(最终浓度为50g/l)的水溶液中，使得荧光增白剂的最终浓度范围达到2.5至12.5g/l。
可以将施胶溶液冷却，然后将其倒入实验用施胶压机的移动辊之间并施加到商购的75g/m2 AKD(烷基烯酮二聚体)施胶的、漂白的纸张基片上。在平板烘干机中，于70℃下将处理过的纸张干燥5分钟。可以对干燥的纸张进行调节，接着在校准的Elrepho分光光度计上测量CIE白度。
在不存在氯化镁，即仅存在荧光增白剂的钠盐，和用等量的氯化钙代替氯化镁的情况下重复本实施例。
结果总结于表1中，其清楚地证明为了达到更高的白度水平，使用氯化镁优于使用氯化钙并且优于仅使用荧光增白剂的钠盐。通过观察到其它二价族II金属离子的氯盐，诸如氯化钙，甚至对荧光增白剂的增白效果具有负面影响来进一步说明了本发明的令人惊讶的性质。
表1
Figure BPA00001229579400051
实施例2
通过如下方式制备施胶组合物：在60℃下以这样的量将式(3)的荧光增白剂添加至搅拌的氯化镁(最终浓度为8g/l)和阴离子型氧化马铃薯淀粉(购自AVEBE B.A.的Perfectamyl A4692)(最终浓度为50g/l)的水溶液中，使得荧光增白剂的最终浓度范围达到2.0至10.0g/l。
可以将施胶溶液冷却，然后将其倒入实验室施胶压机的移动辊之间并施加到商购的75g/m2 AKD(烷基烯酮二聚体)施胶的、漂白的纸张基片上。在平板烘干机中，于70℃下将处理过的纸张干燥5分钟。可以对干燥的纸张进行调节，接着在校准的Elrepho分光光度计上测量CIE白度。
在不存在氯化镁，和用等量的氯化钙代替氯化镁的情况下重复本实施例。
结果总结于表2中，其清楚地证明了相较于荧光增白剂仅以钠盐形式存在的情况，使用氯化镁达到更高白度水平的优势。
表2
实施例3
通过如下方式制备施胶组合物：在60℃下以这样的量将式(3)的荧光增白剂添加到搅拌的氯化镁(最终浓度为6.25和12.5g/l)和阴离子型氧化谷物淀粉(最终浓度为50g/l)(Penford Starch 260)的水溶液中，使得荧光增白剂的最终浓度范围达到0至12.5g/l。可以将每份施胶溶液冷却，然后将其倒入实验室施胶压机的移动辊之间并施加到商购的75g/m2 AKD(烷基烯酮二聚体)施胶的、漂白的纸张基片上。在平板烘干机中，于70℃下将处理过的纸张干燥5分钟。
可以对干燥的纸张进行调节，接着在校准的Auto Elrepho分光光度计上测量CIE白度。结果显示在表3中。
实施例4
通过如下方式制备施胶组合物：在60℃下将式(3)的荧光增白剂添加到搅拌的硫代硫酸镁六水合物(最终浓度为10和20g/l)和阴离子型氧化谷物淀粉(最终浓度为50g/l)(Penford Starch 260)的水溶液中，使得荧光增白剂的最终浓度范围达到0至12.5g/l。可以将施胶溶液冷却，然后将其倒入实验室施胶压机的移动辊之间并施加到商购的75g/m2 AKD(烷基烯酮二聚体)施胶的、漂白的纸基片上。在平板烘干机中，于70℃下将处理过的纸干燥5分钟。
可以对干燥的纸进行调节，接着在校准的Auto Elrepho分光光度计上测量CIE白度。结果显示在表3中。
表3
Figure BPA00001229579400091
相较于荧光增白剂仅以钠盐形式存在的情况，该结果清楚地证明了，使用氯化镁或硫代硫酸镁以达到更高白度水平的优势。

Claims (10)

1.用于纸张的施胶组合物，其特征在于，所述施胶组合物含有(a)至少一种式(1)的荧光增白剂
Figure FPA00001229579300011
其中，
R1是氢或SO3M，
R2是氢或SO3M，
R3是氢、C1-4烷基、C2-3羟基烷基、CH2CO2M、CH2CH2CONH2或CH2CH2CN，
R4是C1-4烷基、C2-3羟基烷基、CH2CO2M、CH(CO2M)CH2CO2M或CH(CO2M)CH2CH2CO2M、苄基，或者
R3和R4与相邻的氮原子一起表示吗啉环，并且
M是氢、碱金属阳离子、铵、单甲基-二-C2-C3羟基烷基铵、二甲基-单-C2-C3-羟基烷基铵、被C2-C3羟基烷基单-、二-或三取代的铵，或所述化合物的混合物，
(b)镁盐，以及
(c)粘合剂，其选自原淀粉、酶改性的淀粉和化学改性的淀粉；
对于每份组分(a)存在0.1至15份的组分(b)。
2.根据权利要求1的施胶组合物，其中R3代表氢、甲基、乙基、正丙基、异丙基、β-羟乙基、β-羟丙基、CH2CO2M、CH2CH2CONH2或CH2CH2CN，并且R4代表甲基、乙基、正丙基、异丙基、2-丁基、β-羟乙基、β-羟丙基、CH2CO2M、CH(CO2M)CH2CO2M、CH(CO2M)CH2CH2CO2M或苄基。
3.根据权利要求1和2的施胶组合物，其中对于每份组分(a)存在0.15至10份的组分(b)。
4.根据权利要求1和2的施胶组合物，其中对于每份组分(a)存在0.4至5份的组分(b)。
5.根据权利要求1至4的施胶组合物，其中组分(b)为乙酸镁、溴化镁、氯化镁、甲酸镁、碘化镁、硝酸镁、硫酸镁或硫代硫酸镁。
6.根据权利要求1至4的施胶组合物，其中组分(b)为氯化镁。
7.根据权利要求1至4的施胶组合物，其中组分(b)为硫代硫酸镁。
8.根据权利要求1至7的施胶组合物，其中基于施胶组合物的总重计，粘合剂的量为2至15重量％。
9.纸的荧光增白方法，包括以下步骤
a)将根据权利要求1至8中一项或多项的施胶组合物施加到纸上，
b)干燥处理过的纸。
10.根据权利要求9的方法，包括将消泡剂、蜡乳液、染料和/或颜料添加到所述施胶组合物中的额外步骤。
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