CN102066664A - 用于增白纸张的组合物和方法 - Google Patents
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Abstract
本发明是关于适合用于纸张的表面处理的组合物,其中该组合物含有具有烷基磺酸基的特定荧光增白剂、二价阳离子盐、及载体。该组合物可用于纸张的增白,尤其是用于施胶压机。
Description
技术领域
本发明是关于适合用于纸张的表面处理的组合物,尤其为施胶压榨液(size press liquor),及用于使用该组合物增白纸张的方法。
背景技术
在纸张的制造中,通常进行施胶步骤以实现良好书写及印刷性质及强度。此种施胶步骤一方面,可于纸页形成前,于纸浆中进行(内部施胶)和,另一方面,可于纸页形成后,于施胶压机(size press)中进行。两种方法的结合也是可以的。在纸张的一个或两个制造阶段中,纸浆或纸页的增白通常也利用荧光增白剂(FWA)进行。通常于纸浆施加的情况下,胶料及荧光增白剂是分开施加至纸浆;而表面施胶的情况下,荧光增白剂是加入施胶压榨液且连同施胶压榨液一起施加至纸张。
纸张的表面施胶及增白的组合广泛地用于造纸业。此种方法尤其广泛用于印刷纸及书写纸方面(复印、喷墨印刷、平版印刷等)。对于具有高白度及改良印刷性能的表面施胶纸有持续趋势,结果需要施胶压榨液尽可能有效。US 6,207,258 B1揭示一种使用二价金属盐尤其为氯化钙的改良喷墨印刷性能的组合物及方法。因此为了达成更明亮更鲜明的印刷,尤其为喷墨印刷,造纸业今日在施胶压榨液中使用氯化钙。但使用该种盐对施胶压榨液中常用的荧光增白剂性能造成不良影响。尤其,增白效果减低,色调偏向绿黄方向,额外观察得荧光的损耗。
出乎意外地,发现含烷基磺酸基的特定双-三嗪基氨基-均二苯代乙烯(bis-triazinylamino-stilbene)化合物当与二价阳离子盐诸如氯化钙组合用于适合纸张的表面处理的组合物诸如施胶压榨液时,可克服现有技术的问题。
发明内容
因此本发明是关于适合用于纸张的表面处理的组合物,其中该组合物含有
(a)至少一种式(I)的荧光增白剂
其中
m及n彼此独立地表示由0至3的整数;
R1、R2、R3、R4、R5及R6彼此独立地表示氢、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4羟烷基,优选为C2-C4羟烷基,其中烷基为直链的或分支的;或R3与R4或R5与R6彼此独立地连同氮原子形成吗啉环、哌啶环或吡咯烷环;或-(CH2)l-SO3M,其中l为1、2或3;或
其中-SO3M基可于邻位、间位或对位及k为由1至3的整数;或-(C1-C4亚烷基)-COOR、-(C1-C4亚烷基)-CONHR、-(C1-C4亚烷基)-COR,优选-(CH2)i-COOR、-(CH2)i- CONHR、-(CH2)i-COR,其中亚烷基为直链的或分支的,i为由1至4的整数,R为C1-C3烷基或等于(equal to)M;
M表示氢、或一当量阳离子尤其为Li、Na、K、Ca、Mg、铵、或通过C1-C4烷基或C2-C4羟烷基所一-、二-、三-或四-取代的铵;
(b)至少一种二价阳离子盐;
(c)至少一种载体;及
(d)水。
本发明是关于用于增白纸张的方法,其中纤维素纸页接触以上界定的组合物,优选该接触是于施胶压机中进行。本发明的优选实施方式在下面详述、权利要求及附图中描述。
附图说明
图1为显示氯化钙对根据实施例1的不同荧光增白剂的性能的影响的图表。
图2为显示不同二价阳离子盐对根据实施例2的不同荧光增白剂的性能的影响的图表。
图3为又一显示氯化钙对根据实施例3的不同荧光增白剂的性能的影响的图表。
具体实施方式
在本发明的优选实施例中,适合用于纸张的表面处理的组合物为施胶压榨液,以及该方法为在施胶压机中用于增白纸张的方法,其中纤维素纸页接触该施胶压榨液。
在本发明的内容中,须了解施胶压机表示表面施加单元,优选为造纸机的表面施加单元,其中所形成的纤维素纸页接触施胶压榨液,以及其中由该纸页所吸收的液体比例(液体吸收)优选可利用辊压来调整。
近来施胶压机或薄膜压机(film press)的发展,也即Speedsizer及Symsizer与Gate-roll,同样被理解为也包括在“施胶压机”术语的范围。
根据本发明,该组合物含有至少一种如上界定的式(I)的双-三嗪基氨基-均二苯代乙烯化合物,其中n、m、R1至R6、及M是如以上定义。在优选实施方式中,n及m为由1至2的整数,最优选为1。于另一个优选实施方式中,R1、R2、R3、R4、R5及R6彼此独立地表示氢、C1-C4烷基、C2-C4羟烷基,其中烷基为直链的或分支的、-(CH2)l-SO3M,l为1、2或3,或
其中该-SO3M基团可于邻位、间位或对位及k为由1至3的整数;更优选n及m为1。在又一个优选实施方式中,R3及R5都为-CH2CH2SO3M,其中优选n及m为1。于另一个优选实施方式中,R1、R2、R4及R6为氢及R3及R5都为-CH2CH2SO3M,其中优选n及m为1。在另一个优选实施方式中,R1、R2、R4及R6为氢及R3及R5都为被两个-SO3M基于2,5-位置取代的苯基,其中优选n及m为1。在另一个优选实施方式中,R1、R2、R4或R6中的至少一个为-(CH2)l-SO3M,l为1、2或3,及R3及R5都为-CH2CH2SO3M。
M的优选实施方式为氢、Na、K、Ca、Mg,其中M为Na或K,最优选为Na。
式(I)的荧光增白剂可根据已知程序制造。例如,GB 1,010,759叙述此种化合物的制备。通常该化合物是经由氰尿酰氯与4,4’-二氨基均二苯代乙烯-2,2’-二磺酸或其盐、及适当磺酸衍生物例如氨基烷-磺酸或其盐反应而制备。
本发明组合物可含有多于一种,优选二种或三种,最优选三种式(I)的荧光增白剂。
除了至少一种式(I)的荧光增白剂外,该组合物的组分(a)可以含有一种或多种已知的双-三嗪基氨基-均二苯代乙烯或以联苯乙烯基-联苯为基础的荧光增白剂。
本发明的组合物中的组分(b)盐包含二价阳离子,优选碱土金属阳离子,尤其钙或镁阳离子。优选二价阳离子的抗衡离子为一价或多价阴离子,尤其为卤阴离子、硫酸根、硫酸氢根、磷酸根、磷酸氢根、磷酸二氢根、碳酸根、碳酸氢根、硝酸根、乙酸根或其混合物,优选为氯阴离子或硫酸根,及最优选为氯阴离子。揭示于US 6,207,258 B1的盐也是适宜的。优选盐为氯化钙、氯化镁、硫酸镁、或其混合物;更优选为氯化钙、氯化镁、或其混合物;及最优选为氯化钙。
组分(c) 的载体为现有技术中已知适合用作为载体的任何化合物,特别地适合用于施胶压榨液的载体。优选载体为羧甲基纤维素(CMC)、聚乙烯醇(PVA)、淀粉或其混合物,而以淀粉为特别优选的。适当载体物质例如为具有可形成氢桥键的能力的亲水性聚合物。优选载体物质为淀粉、聚乙烯醇类、羧甲基纤维素类及具有由200至8000g/mol的数均分子量的聚乙二醇类,及这些物质的任何期望的混合物,这些聚合物任选地可被改性。优选聚乙烯醇具有>85%的水解度,优选羧甲基纤维素为具有>0.5的取代度DS的那些。以具有由200至8000g/mol的数均分子量的聚乙二醇为特被优选的。适当淀粉例如但非排它地是基于马铃薯淀粉、稻米淀粉、小麦淀粉、玉米淀粉或木薯淀粉。尤其,其分子量已经通过部分降解而降低或已通过衍生获得的淀粉优选替代天然淀粉使用。此外,两种改性步骤,即已经部分降解和另外经衍生,相结合的淀粉是合适的。典型淀粉降解的方法例如为酶促处理、氧化处理、热处理或水解处理。适当淀粉衍生物的实例为羟乙基淀粉或阳离子淀粉。
本发明组合物含有水作为其组分(d),任选可含有施胶剂,适当施胶剂为烯基乙烯酮二聚物、烷基乙烯酮二聚物(AKD)、烯基丁二酐(ASA)、松香胶料、苯乙烯顺丁烯二酐共聚物、苯乙烯丙烯酸酯、苯乙烯丙烯酸共聚物、聚氨酯或乙烯丙烯酸共聚物或其它常用纸张化学品诸如苯乙烯基-丙烯酸酯共聚物、胶乳、颜料、消泡剂、或盐类诸如氯化钠或碳酸氢钠、或其中二种或多种的混合物。
以组合物的100wt%为基准,本发明组合物优选含有0.02至3,更优选0.05至2,及最优选0.1至1wt%的量的组分(a)。若使用式(I)的那些化合物以外的荧光增白剂,则以100wt%组分(a)为基准,其用量为5至95wt%。以100wt%组合物为基准,组分(b)的优选含量为0.2至8,尤其为0.5至6,及最优选为1至5wt%。以100wt%组合物为基准,组分(c)的优选含量为3至20,尤其为5至15,及最优选为6至12wt%。以100wt%组合物为基准,本发明组合物优选含有75至96.78,尤其79至94.45,及最优选82.5至92.9 wt%含量的水。
任选地,以100 wt%组合物为基准,该组合物可含有0至5,尤其0至4,及最优选0至3 wt%含量的施胶剂。
此外,相对小量通常低于5wt%的量的额外辅剂诸如分散剂、增稠剂、抗冻剂、防腐剂、络合剂等或得自荧光增白剂合成过程未于后处理(working-up)中完全移除的有机副产物可含于本发明组合物。
适当组合物也在US 6,207,258 B1中描述,其中根据本发明,使用至少一种式(I)的荧光增白剂作为组分(a)。
组合物的制造可通过已知方法执行,优选是通过组合用作为组分(a)的荧光增白剂的水溶液,其优选具有适当pH值,与其它组分,诸如载体物质、施胶剂、粘结剂、颜料、盐类或标准化剂而执行。优选,制备载体组分(c)的水性制剂,于此制剂中添加盐组分(b)的水性制剂,接着添加荧光增白剂组分(a)的水性制剂,该制剂优选是以适当pH值调整,及添加其它组分。
本发明的用于增白纸张的方法是根据已知方法优选使用施胶压机进行但非限制性。所使用的纸张并无特殊限制,可为任意纤维素纸页。
通过本发明方法获得的纸张除了具有改良的印刷性能外,具有改良的白度,因而尤其适合用于喷墨印刷应用。
所制造的纸张的白度可通过CIE白度加以特征化。当根据CIE白度测定时,不同的荧光增白剂可针对饱和行为(saturation behavior)彼此比较。换而言之,若使用更大量荧光增白剂,而未发现白度的进一步增高,则属饱和行为,当使用更高量时甚至对白度造成不良影响。饱和效应也称作为绿化(greening)。绿化极限,即荧光增白剂用量增加实质上不会导致白度进一步增高的该点,可由a*-b*图导出,其中a*及b*为CIE-L*a*-b*体系中的色坐标。
下列实施例举例说明本发明且显示优选实施方式但非限制本发明的范围。
实施例
实施例1
在氯化钙存在下,不同荧光增白剂的增白性能是使用下述施胶压机应用的测试程序进行研究。
首先制备中性氧化降解的马铃薯淀粉的15%淀粉溶液(Perfec-tamyl 4692)及50%氯化钙溶液。使用的纸张为80克/平方米原纸(base paper),该纸为机制纸,经内部施胶(柯伯(Cobb)等于110克/平方米)且使用荧光增白剂略微增白而具有如下光学特性:CIE-104.89;L*=93.92;a*=1.21;b*=-4.34。
在玻璃杯中称重荧光增白剂,添加13.33克15%淀粉溶液。然后称重加入50%氯化钙溶液,溶液以水填补至20克,因此测试是于10%淀粉溶液中进行。短时间搅拌后,溶液通过具有Rakel (2号)的半自动实验室涂布机施加至该原纸一面上,该涂布机可模拟薄膜压机的施加。施加1.7克/平方米的干淀粉至该原纸上。在拉伸后,该纸张在干燥滚筒上在约100℃下直接干燥。在气候适应(climatization)隔夜后,纸张的加工面(prepared side)使用Datacolor光谱仪(ISO2469)通过测定CIE、L*、a*及b*测量,使用的光源是遵照ISO2469标准。
对于每100克淀粉制剂,荧光增白剂的用量分别为0.28克和0.56克;氯化钙用量分别为0克和2克。使用下列荧光增白剂:
所得结果总结于表1。
表1
由表1可知,根据本发明的含牛磺酸基团即烷基磺酸基团的FWA 1及FWA 2几乎对所使用的全部荧光增白剂的浓度,都显示出通过氯化钙的存在在白度上的改良(△CIE为正值)。这通过例如比较含及未含氯化钙的0.28 wt% FWA的数值可知。另一方面,比较例FWA 1至3显示在白度上的显著降低(△CIE为负值)。为了进一步举例说明,表1的结果也显示于图1的图表中。
前述数据显示使用具烷基磺酸基团尤其牛磺酸基团的双-三嗪基氨基-均二苯代乙烯荧光增白剂化合物,在二价阳离子盐尤其为氯化钙的存在下,导致具有改良白度的纸张。
实施例2
本发明的FWA及比较例FWA的增白性能已经在二价阳离子钙、镁及钡盐(CaCl2、MgCl2及BaCl2)存在下进行研究。
测试程序为实施例1使用的相同测试程序。如下表2所示,以100克淀粉制剂为基准,该盐用量为0克和2克。FWA用量为0.28克/每100g淀粉制剂。
本发明的FWA为具有下式的FWA 3:
FWA 3
供比较用,使用如实施例1所述的比较例1作为FWA。
所得结果在下表2中描述及进一步显示于图2。
表2
前述实验结果证实使用氯化钙及其它二价阳离子盐,获得了在二价阳离子盐存在下的改良增白。
实施例3
研究本发明的不同的FWA及比较例FWA在氯化钙存在下的增白性能。测试程序为实施例1所使用的相同测试程序。以100克淀粉制剂为基准,氯化钙用量为0克和2克,如下表3指示。以100克淀粉制剂为基准,FWA用量为0.28克,也如下表3指示。本发明的FWA为如实施例1所述的FWA1及FWA 2、如实施例2所述的FWA3及另外如下的FWA4:
FWA 4
供比较用,使用如实施例1中所描述的比较例1及比较例2作为FWA。
所得结果说明于下表3及进一步显示于图3中。
表3
Claims (15)
1.适合用于纸张的表面处理的组合物,其中该组合物含有
(a)至少一种式(I)的荧光增白剂
其中
m及n彼此独立地表示由0至3的整数;
R1、R2、R3、R4、R5及R6彼此独立地表示氢、氰基、C1-C4烷基、C1-C4烷氧基、C1-C4羟烷基,优选为C2-C4羟烷基,其中烷基为直链的或分支的;或R3与R4或R5与R6彼此独立地连同氮原子一起形成吗啉环、哌啶环或吡咯烷环;或-(CH2)l-SO3M,其中l为1、2或3;或
,
其中-SO3M基可于邻位、间位或对位及k为由1至3的整数;或-(C1-C4亚烷基)-COOR、-(C1-C4亚烷基)-CONHR、-(C1-C4亚烷基)-COR,优选-(CH2)i-COOR、-(CH2)i- CONHR、-(CH2)i-COR,其中亚烷基为直链的或分支的,i为由1至4的整数,R为C1-C3烷基或等于M;
M表示氢、或一当量阳离子尤其Li、Na、K、Ca、Mg、铵、或通过C1-C4烷基或C2-C4羟烷基所一-、二-、三-或四-取代的铵;
(b)至少一种二价阳离子盐;
(c)至少一种载体;及
(d)水。
2.如权利要求1的组合物,其中n和m为1,及R3和R5都为-CH2CH2SO3M。
3.如权利要求2的组合物,其中R1、R2、R4及R6为氢。
4.如权利要求1的组合物,其中n和m为1,R1、R2、R4及R6为氢,和R3与R5都为通过两个-SO3M基团在2,5-位置取代的苯基。
5.如权利要求1或2的组合物,其中R3和R5都为-CH2CH2SO3M,及R1、R2、R4或R6中的至少一个为-(CH2)k-SO3M,k为1、2或3。
6.如前述权利要求中任一项的组合物,其中M为Na或K。
7.如前述权利要求中任一项的组合物,其中组分(b)的盐为氯化钙。
8.如前述权利要求中任一项的组合物,其中组分(c)的载体是选自羧甲基纤维素、聚乙烯醇、淀粉及其混合物。
9.如权利要求8的组合物,其中该载体为淀粉。
10.如前述权利要求中任一项的组合物,其中该组合物含有0.02至3wt%的量的组分(a),0.2至8wt%的量的组分(b),及3至20wt%的量的组分(c),各自是以100wt%组合物为基准。
11.如前述权利要求中任一项的组合物,其中该组合物为施胶压榨液。
12.如权利要求11的组合物,其中该组合物含有施胶剂。
13.用于增白纸张的方法,其中纤维素纸页接触如前述权利要求中任一项所界定的组合物。
14.如权利要求13的方法,其中该接触是在施胶压机中进行。
15.通过如权利要求13或14的方法获得的纸张。
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