CN101553531B - 荧光增白剂水溶液 - Google Patents

荧光增白剂水溶液 Download PDF

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CN101553531B
CN101553531B CN2007800292347A CN200780029234A CN101553531B CN 101553531 B CN101553531 B CN 101553531B CN 2007800292347 A CN2007800292347 A CN 2007800292347A CN 200780029234 A CN200780029234 A CN 200780029234A CN 101553531 B CN101553531 B CN 101553531B
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M·高托
A·C·杰克森
A·S·廷达尔
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
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    • 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
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Abstract

本发明涉及低粘度的储存稳定的荧光增白剂/PVOH水溶液，其可以由造纸者直接使用，因为它们可以由泵直接计量送入涂层组合物中，并且其提供具有出人意料的高白度的涂布纸。

Description

荧光增白剂水溶液
本发明涉及具有聚乙烯醇的荧光增白剂水溶液，其能够由造纸者直接使用并且其提供高白度的经涂覆的纸(coated papers)。
众所周知，经涂覆的纸的白度和因而吸引力能够通过向涂层组合物中添加荧光增白剂而得到改善。为了满足对具有更高白度的经涂覆的纸的需求，需要更有效的荧光增白剂。
尽管已知聚乙烯醇(PVOH)能够通过作为载体而增强着色的(pigmented)涂层组合物中荧光增白剂的性能(参见，例如Brander的“Surface Application of Paper Chemicals”(Springer，1997)，164页)，但是当造纸者想要使用所述醇时，必须将它单独加入到涂层组合物中，典型地以水溶液的形式，导致涂层组合物较高的水含量并因此导致较长的干燥时间。向造纸者提供完全令人满意的使用作为荧光增白剂载体的PVOH的方式的问题仍然存在。
WO 2005/056658通过公开制备荧光增白剂/PVOH水性浓缩物的方法寻求提供解决方案，所述方法包括相继的以下步骤：(a)提供包括水和荧光增白剂活性成分的水性增白剂组合物，其中所述荧光增白剂活性成分典型地以约10％-约25％的量存在于所述水性增白剂组合物中；(b)将聚乙烯醇树脂与所述荧光增白剂组合物混合，数量为每0.25-10湿份的水性增白剂组合物约1份干聚乙烯醇树脂，从而提供聚乙烯醇树脂和荧光增白剂的初期水性浓缩物(nascent aqueous concentrate)；和(c)蒸煮(cooking)所述水性浓缩物以溶解固体(即提供含有荧光增白剂和9.1-80％聚乙烯醇的水溶液)。该方法使得能够不损害亮度和色彩而制备具有较低水含量的着色涂层组合物。
然而，WO 2005/056658并没有为造纸者提供令人满意的解决方案，造纸者典型地希望将荧光增白剂/PVOH溶液直接计量加入涂层组合物；含有荧光增白剂和多于9％的PVOH的水溶液通常具有非常之高的粘度，以至于它们只能困难地泵送，如果能泵送的话。造纸者典型地不能使用粘度大于1,000mPa.s的液体，不仅因为泵送困难，而且还因为当将具有这种高粘度的液体加入涂层组合物时的惊人增稠(shock thickening)。
提供兼具良好的增白能力(brightening ability)和低粘度的荧光增白剂/PVOH水溶液仍是有待解决的问题。
如今发现，可以生产具有低粘度的荧光增白剂/PVOH溶液，其可以由造纸者直接使用，因为它们能够由泵直接计量加入到涂层组合物中，并且其提供具有令人惊奇的高白度的经涂覆的纸。
因此，本发明提供基本上由以下物质组成的荧光增白剂水溶液：
(a)10-50wt％的至少一种式(1)的荧光增白剂
Figure G2007800292347D00021
其中
M是氢、碱金属原子、铵或衍生自胺的阳离子，优选是氢或钠，最优选是钠，
R1是氢、C1-C4烷基或C2-C4羟烷基，和
R2是C1-C4烷基，其可被-CN或-CONH2基团取代，或C2-C4羟烷基，或
R1和R2与氮原子一起形成吗啉代环；
(b)0.5-9wt％的水解度为60-85％的聚乙烯醇；和
(c)水。
NR1R2优选是N(CH2CH2OH)2、N(CH2CH(CH3)OH)2、N(CH2CH2OH)CH2CH2CONH2或N(CH2CH(CH3)OH)CH2CH2CONH2，和最优选是N(CH2CH2OH)2或N(CH2CH(CH3)OH)2。
所述水溶液可以包含最多10wt％的盐，典型地是氯化钠，作为来自荧光增白剂生产的副产物形成。
所述水溶液还可以含有一种或多种防冻剂、生物杀灭剂、络合剂或其它添加剂，和在荧光增白剂制备过程中形成的有机副产物。所述水溶液还可以含有其它载体，如聚乙二醇。
聚乙烯醇优选具有65-80％的水解度和2-40mPa.s的布氏粘度(Brookfield viscosity)(在20℃的4％水溶液)。更优选地，聚乙烯醇具有范围在65-75％的水解度和2-20mPa.s的布氏粘度(在20℃的4％水溶液)。
优选地，所述溶液的聚乙烯醇含量为溶液重量的1-5％，更优选地1.5-4％。
荧光增白剂在所述溶液中的浓度优选为溶液重量的15-40％，更优选地18-35％。
所述荧光增白剂/PVOH溶液典型地通过将聚乙烯醇作为固体加入到荧光增白剂在水中的搅拌溶液中，并加热到90-95℃直到形成透明溶液来制备。
所述水溶液的pH值优选为从中性到明显的碱性，特别是在pH 7-pH10的范围。如果需要，可以通过添加M-对应的碱(M-corresponding bases)如碱金属氢氧化物或碳酸盐、氨或胺调节pH值。
本发明的荧光增白剂/PVOH溶液存储稳定，并且由于它们可以由泵直接计量加入涂层组合物，所以可以原样直接使用。因此，本发明的进一步的目的是将增白剂/PVOH溶液加入到涂层组合物中，以获得经涂覆和经荧光增白的纸。
因此，本发明还提供用于生产至少在涂层中被荧光增白的经涂覆的纸的方法，其中在纸张形成(sheet formation)后将如上所述的涂层组合物涂覆到纸上。
所述涂层组合物基本上是含有至少一种粘合剂，和白色颜料，特别是遮盖白色颜料(opacifying white pigment)的水性组合物，并且可以另外含有进一步的添加剂如分散剂、消泡剂和合成增稠剂。
尽管可以生产不含白色颜料的涂层组合物，但是用于印刷的最好的白色基底是使用含有10-70wt％的白色颜料的不透明涂层组合物制造的。此类白色颜料通常是无机颜料，如硅酸铝(高岭土，或者称为瓷土)，碳酸钙(白垩)、二氧化钛、氢氧化铝、碳酸钡、硫酸钡，或硫酸钙(石膏)。
所述粘合剂可以是任何通常用在造纸业中用于生产涂层组合物的那些，并可以由单一粘合剂组成或由主粘合剂和次要粘合剂的混合物组成。优选地，所述唯一或主粘合剂是合成胶乳(synthetic latex)，典型地是苯乙烯-丁二烯、醋酸乙烯酯、苯乙烯丙烯酸类(styrene acrylic)、乙烯基丙烯酸类(vinyl acrylic)或乙烯醋酸乙烯酯聚合物。所述次要粘合剂可以是例如淀粉、羧甲基纤维素、酪蛋白(casein)、大豆聚合物(soypolymers)、聚乙烯醇或任何上述物质的混合物。
所述唯一或主粘合剂的使用量典型地为白色颜料重量的5-25％。所述次要粘合剂的使用量典型地为白色颜料重量的0.1-10％。
式(1)的荧光增白剂的使用量典型地为白色颜料重量的0.01-1％，优选地为白色颜料重量的0.05-0.5％。
实施例
以下实施例将更详细地解释本发明。如果不另外说明，“％”和“份”都按重量计；粘度使用布氏粘度计测定。
制备实施例1
荧光增白剂溶液1通过以下方式生产：将
25.9份式(2)的荧光增白剂，
72.0份水，和
2.1份水解度为71％和布氏粘度为5.4mPa.s(在20℃的4％水溶液)的聚乙烯醇
一起搅拌，同时加热到90-95℃，直到获得透明溶液，其在冷却到室温后保持稳定。将溶液的pH用氢氧化钠调整到9.0。
Figure G2007800292347D00041
溶液的粘度在20℃为97mPa.s，在10℃为211mPa.s。
制备实施例2
对比实施例(不含聚乙烯醇)
荧光增白剂溶液2通过以下方式生产：将
25.9份式(2)的荧光增白剂，和
74.1份的水一起搅拌。用氢氧化钠将溶液的pH调节到9.0。
应用实施例
制备涂层组合物，其含有500份白垩(可从OMYA以商品名Hydrocarb 90购得)、500份粘土(可从IMERYS以商品名Kaolin SPS购得)、470份水、6份分散剂(聚丙烯酸的钠盐，可从BASF以商品名PolysalzS购得)、200份50％胶乳(苯乙烯丁二烯共聚物，可从Dow以商品名DL921购得)和50份10％的羧甲基纤维素(可从Noviant以商品名Finnfix 5.0购得)的水溶液。通过添加水将固体含量调节到60％，并用氢氧化钠将pH调整到8-9。
将分别如制备实施例1和2中所述制备的荧光增白剂溶液1和2，以干固体重量的0.4-1.0％的浓度范围加入搅拌的涂层组合物中。然后使用具有标准速度设定和标准棒上负荷的自动绕线棒施加器(wire-woundbar applicator)将经增白的涂层组合物施加到商业75gsm中性施胶白纸基片(commercial 75gsm neutral-sized white paper base sheet)上。然后将经涂覆的纸在热空气流中干燥5分钟。调理(condition)经干燥的纸，然后在经校准的Elrepho分光光度计上测定CIE白度。
表1
  OBA溶液占干固体重量的浓度(％)   OBA(2)占干固体重量的浓度(％)  使用溶液1的CIE白度  使用溶液2的CIE白度(对比)
  0.4   0.104  88.7  86.9
  0.6   0.155  89.9  88.2
  0.8   0.207  91.8  89.1
  1.0   0.259  92.7  88.5
结果清楚地显示使用仅含有2.1wt％聚乙烯醇的本发明溶液制备的经涂覆的纸在白度方面惊人的优越性。
制备实施例3-5
含有12.3％活性增白剂的荧光增白剂溶液3-5通过以下方式生产：将
12.3份式(2)的荧光增白剂，
(87.7-x)份水，和
x份水解度为85.2％和布氏粘度为3.7mPa.s(在20℃的4％水溶液)的聚乙烯醇
一起搅拌，同时加热到90-95℃，直到获得透明溶液，其冷却到室温后保持稳定。用氢氧化钠将各溶液的pH调节到9.0。将各溶液的粘度记录在表2中。
表2
  实施例编号   占溶液重量的PVOH浓度(％)   粘度(20℃)   粘度(10℃)
  3   3.2   21.6   34.4
  4   6.3   123.5   256.4
  5(WO 2005/056658的实施例)   9.5   4269   5089
结果清楚地显示就较低的粘度并从而就可泵送性(pumpability)而言本发明溶液的优势。

Claims (8)

1.荧光增白剂水溶液，基本由以下物质组成：
(a)18-35wt％的至少一种式(1)的荧光增白剂
其中
M是氢、碱金属原子、铵或衍生自胺的阳离子，
R1是氢、C1-C4烷基或C2-C4羟烷基，和
R2是C1-C4烷基，其可被-CN或-CONH2基团取代，或C2-C4羟烷基，或
R1和R2与氮原子一起形成吗啉代环；
(b)1.5-4wt％的水解度为65-75％的聚乙烯醇；和
(c)水。
2.根据权利要求1的溶液，其中
M是钠，
NR1R2是N(CH2CH2OH)2、N(CH2CH(CH3)OH)2、N(CH2CH2OH)CH2CH2CONH2或N(CH2CH(CH3)OH)CH2CH2CONH2，和
其中所述聚乙烯醇在20℃的4％水溶液中具有2-40mPa.s的布氏粘度。
3.根据权利要求1的溶液，其中
M是钠，
NR1R2是N(CH2CH2OH)2或N(CH2CH(CH3)OH)2，和
其中所述聚乙烯醇在20℃的4％水溶液中具有2-20mPa.s的布氏粘度。
4.根据上述权利要求任意一项的溶液用于纸用涂层组合物的用途。
5.用于生产经涂覆的纸的方法，其中在纸张形成后将含有根据权利要求1-3任意一项的溶液的涂层组合物涂覆在纸上。
6.根据权利要求5的方法，其中所述涂层组合物含有10-70wt％的一种或更多种白色颜料。
7.根据权利要求5或6的方法，其中所述涂层组合物含有基于合成胶乳的主粘合剂，所述合成胶乳选自苯乙烯-丁二烯、醋酸乙烯酯、苯乙烯丙烯酸类、乙烯基丙烯酸类或乙烯醋酸乙烯酯聚合物，或者附加的选自淀粉、羧甲基纤维素、酪蛋白、大豆聚合物或聚乙烯醇或任何上述物质的混合物的次要粘合剂。
8.根据权利要求7的方法，其中所述主粘合剂的使用量为白色颜料的5-25wt％，其中所述次要粘合剂的使用量为白色颜料的0.1-10wt％，和其中式(1)的荧光增白剂的使用量为白色颜料的0.01-1wt％。
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