CN100506920C - 含有板状分层的硅酸盐颜料的涂层和填充物组合物 - Google Patents
含有板状分层的硅酸盐颜料的涂层和填充物组合物 Download PDFInfo
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Abstract
本发明涉及含有板状麦羟硅钠石颜料的涂层组合物;含有板状麦羟硅钠石颜料的纸产品;含有板状麦羟硅钠石和选自聚丙烯酸酯聚合物、聚乙烯醇聚合物、含马来酸酐的共聚物或多磷酸盐的悬浮剂以及选自苯乙烯丁二烯聚合物、丙烯酸酯聚合物、羟化的丙稀腈丁二烯聚合物、聚氯乙稀、polyvinyledenechloride、聚苯乙烯、氟化的聚乙烯或聚丙烯、或四氟乙烯的乳胶聚合物的乳胶分散体或乳液的水性悬浮液;以及含有板状分层硅酸盐的制品或配方。
Description
背景技术
本发明涉及涂层组合物及其最终用途。
通常对纸进行涂层以增加其美感。纸的颜料是现代纸涂层和表面浆料技术中不可缺少的部分。在造纸工业中公知的多种多样的颜料,如二氧化钛、碳酸钙、滑石、合成的硅酸盐以及粘土、如皂土和瓷土适于用作纸的填充物和/或涂层。瓷土,一种自然界中存在的氢氧化铝酸盐硅酸酯,是目前被最广泛使用的,并且在目前可得到各种颗粒尺寸和光亮度的瓷土。
令人惊奇的是在造纸工业中除了磁粘土以外,很少用到硅或硅酸盐的无机颜料。硅和硅酸盐以及其他颜料,如TiO2,小于纸颜料的百分之三。在造纸工业中,使用高构造的无定形硅颜料来取代、至少部分取代TiO2,或改善吸墨性。例如,详见G.Alderfer and R.Crawford,Chapter 12-“High Structure Amorphous Silica Pigments in Paper”,inPigments for Paper/edited by R.W.Hagemeyer,TAPPI PRESS 1997.
理想地,提供一组基于硅或硅酸盐的合成纸颜料,并且其具有可生产适合于印刷、食品包装和其他工业的高质量纸产品的多种特性。
发明概述
在第一方面,本发明涉及含有板状麦羟硅钠石颜料的涂层组合物。
在第二方面,本发明涉及含有板状麦羟硅钠石颜料和另一个选自以下的颜料的混合物的涂层组合物:碳酸钙、沉淀的碳酸钙(PCC)、瓷土、滑石、氢氧化铝或二氧化钛。
在第三方面,本发明涉及含有板状麦羟硅钠石颜料的纸制品。
在第四方面,本发明涉及含有板状麦羟硅钠石和选自以下的其他共聚物的悬浮剂的水性悬浊液:聚丙烯酸酯聚合物、聚乙烯醇、多磷酸盐或苯乙烯共聚物或马来酸酐酯或马来酸酐。
在本发明的一个优选具体实施方案中,本发明涉及包含所述的板状分层硅酸盐、悬浮剂和乳胶聚合物的涂层组合物。
在本发明的又一优选具体实施方案中,本发明涉及包含所述的板状分层硅酸盐、悬浮剂和选自淀粉、纤维素或蛋白的粘合剂的涂层组合物。
在第五方面,本发明涉及含有板状麦羟硅钠石、悬浮剂、和选自以下的乳胶聚合物或粘合剂的悬浊液:例如,苯乙烯-丁二烯胶乳、苯乙烯-丙烯酸盐乳胶、苯乙烯-丁二烯-丙烯腈乳胶、苯乙烯-马来酸酐乳胶、苯乙烯-丙烯酸盐-马来酸酐乳胶、多糖、蛋白质、聚乙烯吡咯啉、聚乙烯醇、聚乙烯乙酸、纤维素或纤维素的衍生物。
术语“乳胶聚合物”在这里指水中聚合物的胶质分散体,其含有分散在水相的阳离子、阴离子或非离子聚合物以及乳化剂。
在第六方面,本发明涉及含有选自板状麦羟硅钠石、板状kenyaite、板状辛硅酸盐、板状KHSi2O5、板状Na2Si2O5、板状滑石、板状CaCO3、板状皂土、板状云母、板状缎光白、板状蛭石或其他板状颜料的分层硅酸盐颜料的涂层组合物。
将在以下的详细描述以及权利要求中明确本发明的其他方面。
在本文中,术语“板状麦羟硅钠石”是指一种具有板状形态的晶状硅酸钠,其具有基本上为平板的结构,侧面尺寸[长和宽]是0.2到10微米,更优选地为0.5到5微米,最优选为1到2微米。
在本文中,术语“分层的硅酸盐”指一种无机物质,如蒙脱石粘土矿。其以许多相邻的、结合的层的形式存在。每层的厚度是大约0.03到大约0.5微米,优选大约是0.1微米。
发明的详细描述
优选地,本发明实践中使用的板状麦羟硅钠石是合成的麦羟硅钠石,其含有超过50重量%的板状麦羟硅钠石,更优选地,超过80重量%,最优选地,超过90重量%的板状麦羟硅钠石。
在热液或亚热液条件下,可由水玻璃(水溶性硅酸钠)、水和氢氧化钠(NaOH)制成板状麦羟硅钠石,以生成具有板状形态的晶体产物,并且类似平玻璃板的晶体,其长约0.2到约10微米,厚度约0.1到约0.1微米。生产出的产品是白色粉末,并且理想地,此板状形态适用于纸上的洁白且光滑的涂层。
可以通过用无机或有机酸滴定,和/或通过用有机表面活性剂处理来调节钠的含量而使板状麦羟硅钠石的表面产生或多或少的亲水或疏水性。这些处理还可以用来使表面具有酸性或碱性的特征。另外,还可以通过表面的硅烷醇(Si-OH)与多种化学物质反应来产生功能性表面基团(Si-OR)而向板状麦羟硅钠石的表面引入多种功能基团,此功能基团可促进板状麦羟硅钠石颜料与纤维素纤维纸型交互作用。
可以用反应活性有机偶联剂,如有机硅烷、乙醇以及四价盐对板状麦羟硅钠石进行改性,从而为纸产品提供独特的表面特性,如光的及粘附的特性。
板状麦羟硅钠石以及其制备方法详细描述于共同未决的美国申请系列(系列号10/257487)中,在此被引用作为参考。
本发明的板状麦羟硅钠石颜料可用于多种应用中,例如,聚烯烃纳米组合物中的纳米填充物、油漆颜料配方、聚烯烃催化剂的催化剂载体(齐格勒催化剂和金属茂)、用于含有分散染料-麦羟硅钠石颜料颗粒等的塑料或纺织品纤维中的染料稳定剂。
板状麦羟硅钠石颜料还可以被用在a)双层或多层物品中含有结合有聚合体膜的板状麦羟硅钠石的纸产品,b)用于除纸以外的其他用途中的含有麦羟硅钠石的乳胶产品,如路标中的油漆和膜,c)纸板产品,d)墨产品,e)FR(阻燃剂)中的麦羟硅钠石-乳胶添加剂,f)反应活性有机偶联剂,如有机硅烷、乙醇以及四价盐等改性的麦羟硅钠石,从而来为纸产品提供独特的表面特性,如,光的及粘附的特性。
板状麦羟硅钠石颜料还可以与如乳胶、淀粉的粘合剂、如羧甲基纤维素(CMC)的共同粘合剂和包括润滑剂和表面活性剂、用于制涂层的流变学改性剂和分散剂的其他添加剂一起使用。
板状麦羟硅钠石颜料还可以作为填充剂用于纸制造工艺。
通常可通过将麦羟硅钠石颜料分散于去离子水中来制备本发明的纸涂层组合物。
所用的板状麦羟硅钠石颜料的剂量取决于所需纸涂层的性能,包括纸片光泽、墨光泽、光亮度、不透明性、Helio、粗糙度、CIE洁白度、B-值等;其他颜料,如碳酸钙、瓷土、二氧化钛的相对量;以及其他成分,如乳胶、表面活性剂及分散剂的相对含量。
通常所用的板状麦羟硅钠石颜料的剂量为大约0.1重量%到大约30重量%,更优选为1重量%到30重量%,最优选为3重量%到30重量%,以包括基材纸或原料、纸颜料及粘合剂的纸组合物的重量计。
有利地,通过使用悬浮剂以适用于在纸上涂层的浓度和粘性分散并稳定板状颗粒而使板状麦羟硅钠石颜料悬浮于水中。
本发明实践中所用的悬浮剂包括,例如聚丙烯酸酯聚合体,如DISPEXTMN40、水溶液中聚合酸盐、Allied Colloids Inc的产品、聚乙烯醇,例如,聚乙烯醇103,Air Products的产品、多磷酸盐,如三磷酸钾、六偏磷酸钠、焦磷酸四钠、苯乙烯和马来酸酐酯的共聚物以及其他马来酸酐的共聚物。
优选的悬浮剂是聚乙烯醇、聚丙烯酸酯、含马来酸酐的共聚物树酯和聚磷酸盐。更优选的悬浮剂是聚乙烯醇、聚丙烯酸酯和聚丙烯酯共聚物。最优选的悬浮剂是聚乙烯醇103和DISPEXTMN40。
在本发明实践中所用的悬浮剂的剂量取决于颜料分散剂中的固体含量和固体成分。通常悬浮剂的剂量为大约0.01重量%到大约2重量%,更优选为大约0.05重量%到大约1.0重量%,最优选为大约0.05重量%到大约0.5重量%。以组合物中颜料的重量计。
可用于本发明实践的优选乳胶共聚体分散剂或粘合剂包括,例如,羧化苯乙烯-丁二烯乳胶、羧化苯乙烯-丙烯酸盐乳胶、羧化苯乙烯-丁二烯-丙烯腈乳胶、聚乙烯醇、以及聚乙烯乙酸盐和丙烯酸酯乳胶的羧化共聚物。
本发明实践中可使用的多糖包括,例如,琼脂、藻酸钠和淀粉,其中淀粉包括改性的淀粉,如热改性淀粉、羧甲基淀粉、羟乙基淀粉和氧化的淀粉。
适用于本发明实践中的蛋白质的例子包括白蛋白、大豆蛋白和酪蛋白。
可以将本发明的麦羟硅钠石颜料用于多种其他的应用中,例如,聚烯烃纳米组合物中的纳米填充物、油漆颜料配方、聚烯烃催化剂的催化剂载体(齐格勒催化剂和金属茂)、用于含有分散的染料-麦羟硅钠石颜料颗粒等的塑料或纺织品纤维中的染料稳定剂。
使用以下实施例来对本发明进行描述但并不限制本发明的范围。除非特别指出,所有的份数和百分比为重量百分比。
用于实施例中的术语按如下定义:
DISPEXTM N40:水溶液中聚合酸的盐,其为Allied Colloids Inc.的产品。
CowlTM Mixer:用来使颜料分散并产生稳定浆液的高剪切混合系统。本仪器由Morehouse Industries Inc.制造。
CP 638NA:羧化丙乙烯/丁二烯乳胶,Dow Chemical Company的产品。
RAPTM 501NA:羧化苯乙烯/丁二烯/丙烯腈乳胶,Dow ChemicalCompany的产品。
Roto基材纸:一种用颜料和粘合剂涂层的纸,其适合用RotoGravure印刷工艺进行印刷。
Dow台式刀片涂层机:一种将纸涂层配方涂层到纸张的台式小型涂层机,并且用刀片修改多余的涂层以产生光滑的涂层表面。
实施例1轮转凹版印刷(Roto Gravure)的涂层配方
1)颜料的分散
颜料以占固体物质43%的百分比由分散剂Dispex-N40分散于去离子水中,其中分散剂的剂量为100份干颜料中含0.25份分散剂。将分散剂加入水中,随后一边用Cowl搅拌器搅拌,一边缓慢地加入板状麦羟硅钠石颜料。当将全部板状麦羟硅钠石颜料加入水中后,增加震荡的速率,然后使板状麦羟硅钠石颜料混匀15分钟。
2)纸的涂层配方
通过混匀表1所示的每种涂层配方的不同成分制备几种纸涂层配方。加入流变学改性剂,即羧基甲基纤维素(Finnfix 10)以提供一些可达到所需涂层重量的厚度。在51%的固体,并由NaOH将其pH值调到8.5的情况下,制备配方。
3)样品的制备
用Dow台式刀片涂层机涂抹纸涂层配方。将涂层涂抹到含有轮转基材纸的木头上。最终涂层重量是4.5lbs/3300sq.ft.。
然后用标准实验室等级的超级压光机将被涂层的纸样品超级压光。配方1作为对照在1500磅/线性英尺(pli)及67℃下被压光至目标光泽度。然后将相同的压光条件用于其他的涂层系统。
在测试前将涂层样品放置到持续湿润的条件下。而后测试样品的主要性能,包括光的及印刷的性能。结果如图1-8所示。
检测步骤
1.纸张光泽度 TAPPI检测方法-T480
2.墨光泽度A
3.亮度 TAPPI检测方法-T646
4.不透明性 TAPPI检测方法-T425
5.HelioB
6.粗糙度 TAPPI检测方法-T555
7.洁白度 TAPPI检测方法-T-560
8.CIE B-值 TAPPI检测方法-T-560
9.被涂层纸强度 TAPPI检测方法-T-514
A墨光泽度检测步骤
使用Prufbau适印性测定仪将薄的墨膜涂敷在一纸条上,然后在室温下使墨干燥。而后使用与T480同样的步骤测定印刷样品的墨光泽度(印刷光泽度)。唯一的区别在于所用的墨膜是Prufbau。Prufbau适印性测定仪是德国Prufbau公司的产品。
BHelio检测步骤
用重复性测试(Reprotest)I.G.T.ACII 5适印性测定仪和Helio测定试剂盒涂敷墨膜。
在以下步骤之后用雕刻轮将墨涂敷到纸上。当墨从轮的雕版上转移到纸上时,有些墨并不能从一些小区或雕板上转移出来。其导致在打印后的纸上会有遗漏的墨点。这些现象造成漏点。在印刷纸条20微米的长度内漏点的数量可用作定量测量Roto印刷质量的尺度。漏点的数量越多,印刷质量越差。最佳的数量是0个漏点。
步骤:
1.用Helio检测试剂盒中的绿色橡胶支撑和得自helio测试工具的聚酯薄膜取代背靠IGT的纸板。
2.将支撑盘放置到IGT槽的上部。将斜角刀片连到重力臂上,并将切片放入盘内。对盘进行调整以使刀片与Helio测试轮对齐,并收紧刀片(盘应该是接近垂直的)。
3.以固定速度旋转IGF,设定速度为1.0m/s。记住用固定速度档。
4.初始压力(上部中心)为50千克压(kgf)。
5.将2-3滴Helio测试墨加到具有测量尺度的雕刻轮,旋转旋扭。只有雕板凹处应该显示出铬光泽的色彩。(通过用N-丁基卡必醇乙酸切除凹版印刷墨制备Helio测试墨,其具有75cp布氏粘度或在#4Shell cup.下为23秒。)如果发生品质不匀,清洗轮和IGT的斜面刀片。如果需要保持轮凹内的分布均匀,重复加墨。
6.停下轮子时,将刀片放置于宽边缘的1英尺以内。
7.启动纸条(纸条仅需要夹子使其附着)。
8.从深到浅地数纸条上印刷部分漏点的数量。在有20个漏点处标记纸条。对照组应该有大约60-70个,然后在相同条件下运行其它的样品。如果超出这个范围,调节压力至其合理。(增加压力应该增加20个点的标记)。
9.随机运行样品。测量距离,用毫米作标记。有20个漏点的距离越长,印刷质量越好。
10.用丙酮清洁仪器。
表1:纸涂层配方
包括塑料颜料共100份
配方1-10
*对照
图1-9表示在任何一种配方中、与任何一种乳胶一起使用麦羟硅钠石颜料的结果:
1)更好的光泽度和印刷墨光泽度
2)颜料系统、粘土和碳酸盐配方具有更好的亮度。但是,使用碳酸盐配方具有更好的亮度改善效果。
3)两种颜料系统和两种乳胶具有更好的不透明性。
4)所有不同的系统都有更好的洁白度和更好的蓝色涂层。
5)更好的作为凹版印刷质量尺度的Hellio。这种改善在所有的系统中均很明显。
6)胶印术乳胶如CP638NA证实其在板状麦羟硅钠石颜料的存在下可以改善轮转印刷性能。这不能通过传统的颜料系统实现。
7)如图9所示,很明显具有板状麦羟硅钠石的涂层纸表面有更高的粘合剂需求。这表明使用板状麦羟硅钠石作出的涂层需要稍多的粘合剂,特别是在胶印术印刷过程中。
尽管本发明对优选的实施例,也就是板状麦羟硅钠石进行了特别的描述,可是本发明还包括其他的板状分层硅酸盐,如板状辛硅酸盐、板状kenyaite及相关的材料,如板状KHSi2O5和板状Na2Si2O5。典型地,这些板状分层硅酸盐具有包括基本上为平板的板状外形,该结构长为0.5到10微米,厚度为0.01到0.1微米,或者纵横比为5到1000。
Claims (11)
1.一种含有板状分层硅酸盐颜料的涂层组合物,其中板状分层硅酸盐是含有超过50重量%的板状麦羟硅钠石的合成麦羟硅钠石。
2.根据权利要求1所述的涂层组合物,其中板状分层硅酸盐的剂量为0.1重量%-30重量%,以组合物重量计。
3.根据权利要求1或2所述的涂层组合物,其中板状分层硅酸盐是含有超过80重量%的板状麦羟硅钠石的合成麦羟硅钠石。
4.根据权利要求3所述的涂层组合物,其中板状分层硅酸盐是含有超过90重量%的板状麦羟硅钠石的合成麦羟硅钠石。
5.根据权利要求1所述的涂层组合物,进一步包含选自以下的其它颜料:碳酸钙、瓷土、滑石、三水合氧化铝、二氧化钛、板状皂土、板状云母、板状缎光白或板状蛭石。
6.根据权利要求5所述的涂层组合物,其中所述碳酸钙选自沉淀的碳酸钙或板状CaCO3。
7.根据权利要求5所述的涂层组合物,其中所述滑石是板状滑石。
8.根据权利要求1所述的涂层组合物,其中板状麦羟硅钠石由选自如下的反应活性结合剂改性:有机硅烷、乙醇或四价盐。
9.根据权利要求1-2和5-8任一项所述的涂层组合物,其包含乳胶。
10.一种含有权利要求1-2和5-8任一项所述的涂层组合物的纸或纸板产品。
11.根据权利要求1-2和5-8任一项所述的涂层组合物作为路标用油漆或膜、作为墨或作为阻燃剂组合物的应用。
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US7479264B2 (en) * | 2001-04-12 | 2009-01-20 | The Dow Chmeical Company | Synthetic platy magadiite and octasilicate |
EP1249533A1 (en) | 2001-04-14 | 2002-10-16 | The Dow Chemical Company | Process for making multilayer coated paper or paperboard |
US7473333B2 (en) | 2002-04-12 | 2009-01-06 | Dow Global Technologies Inc. | Process for making coated paper or paperboard |
US7652087B2 (en) * | 2006-02-21 | 2010-01-26 | American Thermal Holdings Company | Protective coating |
KR100903686B1 (ko) * | 2006-05-30 | 2009-06-18 | (주)더블유비이 신소재 | 나노점토를 이용한 친환경 건축내장용 나노복합 도료조성물 및 이의 제조방법 |
CN101501273A (zh) * | 2006-08-14 | 2009-08-05 | 巴斯夫欧洲公司 | 包含硅溶胶的纸涂布组合物 |
EP2017076A1 (en) * | 2007-07-09 | 2009-01-21 | Oppboga Bruk AB | Flame resistant cardboard or fibre laminate |
JP5370360B2 (ja) * | 2008-05-21 | 2013-12-18 | 東亞合成株式会社 | 炭酸カルシウム用分散剤 |
RU2443739C1 (ru) * | 2010-11-02 | 2012-02-27 | Закрытое акционерное общество "Институт прикладной нанотехнологии" | Состав краски с термо-, огнезащитными свойствами |
US11142654B2 (en) | 2010-11-03 | 2021-10-12 | Chemetall Gmbh | Composition and process for the generation of a clear or translucent emissive coating |
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CN105037837B (zh) * | 2015-08-24 | 2017-03-08 | 苏州世名科技股份有限公司 | 适用于天然乳胶制品着色的钛白水性色浆及其制备方法 |
CN106519092B (zh) * | 2016-11-21 | 2019-01-18 | 华南理工大学 | 以有机改性麦羟硅钠石为乳化剂的Pickering乳液制备聚合物纳米复合材料的方法 |
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AU7837198A (en) * | 1997-06-09 | 1998-12-30 | Herberts G.M.B.H. | Aqueous coating composition of a polymer and exfoliated platelet filler |
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