CN101460679B - 改善涂布纸的可印刷性的组合物 - Google Patents
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Abstract
本发明涉及通过在纸上添加包括颗粒状淀粉的组合物,改善涂布纸的可印刷性,所述组合物基本不含矿物或合成颜料。
Description
本发明涉及涂布纸的改善的可印刷性,在一定意义上例如油墨需求减少、较低的油墨擦除和更高的δ光泽。
用涂料颜料涂布纸主要为了改善印刷性能。通过用含有矿物或合成颜料和粘合剂的一层或多层涂布基纸,基纸的较粗糙表面变光滑。涂布纸然后干燥至合适的水分含量并且通常砑光。颜料涂料改善纸性能,例如亮度、不透性、光泽度和光滑度,所有都有助于印刷性能。
高光泽度和光滑度并不总是理想的。过于光泽的纸可能导致印刷的图像或文字不足以与背景区分,因为所谓的δ光泽(印刷和未印刷的区域之间光泽度的差异)过低。过于光滑的表面可能引起印刷中的擦除问题,因为油墨不能足够牢固地吸收/附着于纸上。存在一些解决替代方案使表面更加暗淡或无光泽,例如无光泽(丝绸)砑光机或涂布彩色颜料选择。对于无光泽涂布纸,油墨擦除同样是问题。
在EP-A1-770493中,通过在载体片材的至少一个表面上形成油墨接收层,制造喷墨记录材料。载体片材通过在含有天然浆粕的纸片材表面上熔融层压聚烯烃树脂而制得,所述聚烯烃树脂可以含有白色颜料。油墨接收层含有水溶性树脂和胶态颜料颗粒。
在GB-1499235中,纸片用一种组合物涂布,该组合物包括总固体含量大于40wt%的橡胶状成膜聚合物的胶乳,和每1.0重量份胶乳固体,0.25至25重量份的未凝胶化淀粉颗粒,所述颗粒具有小于纸表面纤维之间平均空隙距离的平均直径。
在EP-A1-1146171中,表面粗糙度低于6微米和表面光泽度为5-80%的纸的δ光泽通过用轻型外涂层涂布,使片材光泽度为50%或更少来改善。外涂层包括流变改性剂/粘合剂组分和平均粒径为200至2000nm的颜料或粘合剂涂布颜料。外涂层为颜料颗粒或其晶簇的局部单层。
在US-5439558中,用含有未凝胶化淀粉颗粒、高岭土、任选的另外的矿物颜料和粘合剂的涂料涂布纸或卡纸。比例为对于全部涂料颜料,淀粉颗粒为2至25wt%,粘合剂为低于12wt%和高岭土为至少60wt%。目的是通过更好的表面涂料覆盖率,减少凹版或轮转凹版印刷中漏点的出现。
在US-5314753中,无光泽印刷纸通过涂布含有25至70wt%碳酸钙作为涂料颜料,10至65wt%未凝胶化淀粉颗粒和至多15wt%粘合剂的组合物来生产。目的是制造一种无光泽涂布印刷纸,其将具有改善的耐洗涤性和对光泽条纹的敏感性更小。
在US-B2-6825252中,涂料组合物包括颜料,例如粘土、碳酸钙、硫化铝酸钙(缎白)、滑石、二氧化钛、硫酸钡、二氧化硅或塑料颜料,和200nm至100μm的离散交联的天然淀粉颗粒的淀粉分散体作为粘合剂。通过在羟基液体存在下,挤出交联淀粉和含水液体的混合物制备分散体。该组合物也可以含有合成乳胶和通常包含在涂料颜料中的附加成分,例如控泡剂、荧光增白剂、流变性添加剂、润湿剂、交联剂、表面活性剂、润滑剂、分散剂和染料。
在US-B2-6833025中,用包括至少65wt%碳酸钙作为矿物颜料和基于矿物颜料计算的0.5至9.5wt%有机颗粒的涂料组合物制造无光泽或丝绸涂布纸,所述颗粒是尺寸为2至50μm的淀粉或石蜡。目的是显著减少油墨磨损倾向,同时获得优良的印刷品光泽度。涂布纸尤其良好地适用于胶版印刷技术。
本发明的目的是提供改善涂布纸可印刷性的新组合物和方法。涂布纸可以是光泽的或无光的(丝绸涂布、无光泽涂布)。这种改善可以表现为例如δ光泽更高(特别是对于光泽纸)、油墨需求更低或油墨擦除更低(特别是对于无光泽涂布纸)。更高的δ光泽可能源于印刷区域的光泽提高和/或未印刷区域的光泽降低。
本发明提供包括颗粒状淀粉的涂料组合物,所述组合物基本不含矿物或合成颜料。令人惊讶的是当施涂于涂布纸时,这种组合物产生改善的印刷性能,因为现有技术解决方案总是从作为必要组分的颜料出发。
涂料组合物以低固含量,优选不超过30%,更优选1至20%和最优选3至15%的固含量施涂于涂布纸。
在纸的一侧上,组合物的量通常为0.1至3g/m2,优选0.2至2g/m2和更优选0.3至0.8g/m2,但是其它量是可能的。
淀粉颗粒可以来源于任何合适的来源,例如土豆、木薯、小麦、玉米、蜡质玉米或燕麦,优选土豆或小麦。颗粒的数均粒度(直径)通常为5至100μm,优选10至80μm,更优选15至60μm和最优选20至50μm。淀粉颗粒优选是未改性的,但是也可以是改性的,例如交联的、稳定的、解聚的、酯化的或醚化的。淀粉颗粒可以为阳离子或阴离子型。
当淀粉为离散颗粒形式时,需要粘合剂来将它们粘合在一起以及将它们粘合到纸表面。可以使用常用的涂料彩色粘合剂,例如聚合物分散体,例如苯乙烯丁二烯、苯乙烯丙烯酸酯或聚乙酸乙烯酯胶乳,或聚合物溶液,例如聚乙烯醇。优选粘合剂为苯乙烯丁二烯胶乳。对于每100重量份淀粉颗粒,粘合剂的量通常为1至20重量份,优选2至10重量份和更优选3至7重量份。
组合物中通常需要流变改性剂来使其稳定,即避免淀粉颗粒沉积。对于每100重量份淀粉颗粒,流变改性剂的量通常为5至50重量份,优选8至40重量份,更优选10至30重量份和最优选15至25重量份。合适的流变改性剂为例如瓜尔胶、羧甲基纤维素(CMC),和碱金属可溶或遇碱金属可膨胀的乳液丙烯酸系共聚物。用例如NaOH将涂料组合物的pH调节至8-10,优选至约9,以便优化流变改性剂的功能。
该组合物可以含有少量矿物或合成颜料,对于每100重量份淀粉颗粒,矿物或合成颜料通常低于20重量份,优选低于10重量份和更优选低于5重量份。但是,最优选该组合物不含这种颜料。
该组合物也可以含有其它添加剂,例如荧光增白剂,交联剂,例如乙二醛或碳酸锆铵,和润滑剂,例如硬脂酸钙。
基纸包括已经通过机械或化学方法或其组合,从木质材料(例如枞松、桦树或桉树)分离的纤维。部分或所有纤维可以属于再循环类型。基纸也可以含有填料(例如碳酸钙、粘土、滑石或白垩)和常用的添加剂以及粘合剂,例如干/湿强剂、排水/保水试剂和疏水性试剂。基纸的克数可以是任何适合于印刷的克数,例如干重为30至200g/m2,优选40至100g/m2。由此纸的定义在此也包括通常分类为纸板或硬纸板的等级。基纸优选以常用的造纸方式生产。通常,基纸干燥至10%含水量并在纸设备上砑光。由此,基纸可以为轻量涂料的典型基纸(所谓LWC基纸)或标准无木基纸(所谓高级纸)。
在施加本发明的组合物(第二涂层或外涂层)之前,至少涂布基纸一次(第一涂层或预涂层)。预涂层可以通过包括刮涂、涂膜或辊输送涂布、喷涂和幕涂的技术以常用方式施涂。涂布可以在纸设备末端进行(在线涂布)或在独立的涂布机上进行(离线涂布)。涂料颜料包括矿物(例如碳酸钙、粘土、滑石或白垩)或合成颜料和粘合剂(例如淀粉或苯乙烯丁二烯胶乳),和可以含有一些常用涂料成分。在纸的一侧,涂布量可以为5至20g/m2,但是其它量是可能的。涂布纸干燥至通常低于10%的合适的水分含量,并且其后可以被砑光。
本发明的组合物施涂在涂布基纸上。对于这一目的,存在许多合适的施涂法,例如刮涂、涂膜或辊输送涂布、幕涂和喷涂。甚至喷涂棒可能是可用的,因为其对平整组合物层来说并不总是必需的。施涂组合物之前,通常将片材干燥至低于10%。但是,一些涂布技术,例如喷涂和幕涂允许在第一涂层(预涂层)已经干燥之前施涂组合物,以及甚至用相同的涂布设备。组合物也可以与涂布基纸的砑光结合施涂。因为片材可能与砑光结合浸湿,现有润湿设备可以用于同时施涂组合物。
涂料和组合物可以仅施涂到纸的一侧,但是更常见的是处理纸的两侧,这种处理甚至可以同时进行。
根据本发明,纸可以由包括平版印刷、凹版印刷或(转轮)凹版印刷、喷墨和电子照相术的技术印刷。优选的印刷方法为平版印刷,因为在δ光泽度、油墨需求和特别是油墨擦除意义上,本发明受益最大。
本发明在以下情况中工作非常良好,并产生印刷性能改善的纸。从包括60%机制浆粕(云杉)和40%化学浆粕(松树)的原料及常用粘合剂和添加剂在造纸机上以传统方式生产60g/m2干重的基纸,干燥至8%含水量并砑光。用62%干重的涂料颜料分散体刮涂该基纸,产生10g/m2干重的层,其包括等量的粘土和研磨碳酸钙(GCC)颜料、每100pph颜料,12份(pph)苯乙烯丁二烯(SB)胶乳,和少量常用涂料颜料添加剂。涂布纸被干燥至8%含水量并轻柔地砑光。以1g/m2干重的量由薄膜输送涂布机将本发明的7%干重水性组合物施涂到涂布基纸上。该组合物含有100pph平均粒径为35μm的未改性的颗粒状马铃薯淀粉,23pph碱金属可溶丙烯酸系共聚物乳液和5pph苯乙烯丁二烯(SB)胶乳。然后将纸干燥至6%含水量并砑光至30%光泽度。最后对纸进行平版印刷。
实施例
以下实施例举例说明本发明,但并不拟在实质上进行限制;除非另有说明,份数和百分比按干重计。
实施例1
由刮刀涂布机以1300m/min的涂布速度将三种涂料颜料以10g/m2的量施涂在基纸上。差别在于颜料选择(粘土或研磨碳酸钙颜料),所有 其它组分(例如胶乳、流变改性剂和光学增亮剂)相同。使用的光泽粘土为用于光泽纸的小颗粒特种粘土,约90%的颗粒小于0.5μm。根据颗粒的正态分布筛选过度研磨碳酸钙(GCC),颗粒为接近一种没有小和大片段的尺寸。将涂布的纸干燥至5%含水量,并保持未砑光。
通过薄膜输送涂布机以1000m/min的速率将少量(0.5g/m2)本发明的组合物施涂于涂布纸上。该组合物含有100pph平均粒径为41μm的颗粒状马铃薯淀粉,4pph苯乙烯丁二烯胶乳和20pph固含量为5%的流变改性剂水溶液。将纸再次干燥至5%含水量。
然后将一半涂布卷轴轻柔地砑光至低光泽度,另一部分保持未砑光。来自造纸厂的商用无光泽砑光涂布纸用作参照物。未砑光纸比参照物具有更低的平滑性,但砑光的处于相同水平。
用砑光纸和砑光纸进行两个独立的实验。在第一个实验中,将纸印刷(B100,黑色100%覆盖率)至油墨密度1.4,测量所需油墨量。在第二个实验中,使用油墨密度1.75,测定未印刷和印刷区域的光泽度(75℃)。以下表格中收集参数和结果(砑光/未砑光的):
纸A 纸B 纸C 对照物
光泽粘土 50 pph
普通粘土 30 40 pph
过度的GCC 70 50 pph
普通GCC 60 pph
SB胶乳(Tg 30℃) 11.5 11.5 11.5 pph
油墨需求* 1.20/1.22 1.15/1.191.20/1.271.41 g/m2
光泽度(未印刷)** 43/39 44/39 40/3131 %
光泽度(印刷的)** 74/69 73/65 73/6358 %
*油墨密度1.4**油墨密度1.75(都为B100,黑色100%覆盖率)
根据本发明,与参照物造纸厂纸相比,未砑光纸和砑光纸都具有明显更低的油墨需求。此外印刷光泽度更好,特别是对于砑光纸。
实施例2
由刮刀涂布机以1200m/min的涂布速度将三种涂料颜料以10g/m2的量施涂在基纸上。差别在于颜料选择和SB胶乳类型,所有其它组分(例如流变改性剂、光学增亮剂等)相同。将涂布的纸干燥至5%含水量并砑光。
通过薄膜输送涂布机以1000m/min的速率将少量(0.5g/m2)本发明的组合物施涂于涂布纸上。该组合物含有100pph平均粒径为41μm的颗粒状马铃薯淀粉,4pph苯乙烯丁二烯胶乳和20pph固含量为5%的流变改性剂水溶液。将纸再次干燥至5%含水量。纸表面光泽度较低,并且不如前述光滑。
来自造纸厂的商用无光泽砑光涂布纸用作参照物。
印刷该纸(B100,油墨密度1.75),测定印刷区域的光泽度(75℃)以及油墨擦除。以下表格中收集参数和结果:
纸A 纸B 纸C 参照物
光泽粘土 50 pph
普通粘土 20 30 pph
过度的GCC 50 80 pph
普通GCC 70 pph
SB胶乳(Tg 30℃) 11.5 11.5 pph
SB胶乳(Tg 10℃) 12.0 pph
光泽度(印刷的) 64 73 73 58 %
油墨擦除 2.7 1.6 0.9 4.4
印刷的光泽度比造纸厂纸具有的光泽度好的多。油墨擦除明显得到改善。
实施例3
由刮刀涂布机以1300m/min的涂布速度,以10g/m2的量将含有光泽粘土40pph、过度的碳酸钙60pph和SB胶乳11.5pph的涂料颜料施涂在基纸上,并干燥至5%含水量。
通过薄膜输送涂布机以1000m/min的速率将0、0.5g/m2和2g/m2本发明的组合物施涂于涂布纸上。该组合物含有100pph平均粒径为41μm的颗粒状马铃薯淀粉,4pph苯乙烯丁二烯胶乳和20pph固含量为10%,pH 9的流变改性剂水溶液。再次将纸干燥至5%含水量,并穿过辊温为40℃和辊隙压力为60kN/m的机械压延机。
测量以下性能:500份复制印刷之后,L&W透气性,拾取和剥离(IGT1.5m/s,中等粘度油),Emtec(疏水性)和未印刷/印刷的光泽度(4彩色黑色)。以下表格中收集结果:
组合物的量 0 0.5 2 g/m2
L&W透气性 7.25 4.88 4.73 ml/min
拾取 0.54 0.68 1.02 m/s
剥离 1.28 1.26 ----- m/s
5/10/15秒下的Emtec 34/12/6 58/30/13 65/38/21 %
未印刷/印刷的光泽度 22.9/45.4 22.6/47.4 19.7/42.1 %
未印刷/印刷的平滑度 4.49/4.15 4.84/4.30 6.60/5.90 μm
这些结果表明本发明降低纸的透气性,改善纸的干燥表面强度,提高纸的疏水性,和提高纸的平滑度。
Claims (29)
1.改善涂布纸可印刷性的组合物,包括颗粒状淀粉、流变改性剂和至少一种粘合剂,其中颗粒状淀粉具有5至100μm的平均粒径;
其中对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于20重量份。
2.根据权利要求1的组合物,其中对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于10重量份。
3.根据权利要求1的组合物,其中对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于5重量份。
4.根据权利要求1的组合物,其中所述组合物不含所述颜料。
5.根据权利要求1的组合物,其中颗粒状淀粉具有10至80μm的平均粒径。
6.根据权利要求5的组合物,其中颗粒状淀粉具有15至60μm的平均粒径。
7.根据权利要求6的组合物,其中颗粒状淀粉具有20至50μm的平均粒径。
8.根据权利要求1的组合物,其中粘合剂为聚合物分散体或聚合物溶液。
9.根据权利要求8的组合物,其中聚合物分散体是苯乙烯丁二烯胶乳。
10.根据权利要求8的组合物,其中聚合物溶液是聚乙烯醇。
11.根据权利要求1-10任一项的组合物,其中流变改性剂为瓜尔胶、羧甲基纤维素或碱金属可溶或遇碱金属可膨胀的乳液丙烯酸系共聚物或这些的任何混合物。
12.改善涂布纸可印刷性的方法,通过在纸上施涂含有至少一种粘合剂的组合物,其中该组合物含有颗粒状淀粉和流变改性剂,对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于20重量份,其中所述组合物以0.1至3g/m2的量施涂。
13.根据权利要求12的方法,其中对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于10重量份。
14.根据权利要求12的方法,其中对于每100重量份淀粉颗粒,所述组合物含有的矿物或合成颜料低于5重量份。
15.根据权利要求12的方法,所述组合物不含所述颜料。
16.根据权利要求12的方法,其中所述组合物以0.2至2g/m2的量施涂。
17.根据权利要求16的方法,其中所述组合物以0.3至0.8g/m2的量施涂。
18.根据权利要求12-17中任一项的方法,其中所述组合物通过薄膜/辊输送机、喷涂、幕涂或刮涂来施涂。
19.纸,包括含有矿物或合成颜料和至少一种粘合剂的第一涂层,所述第一涂层为预涂层,和含有至少一种粘合剂的第二涂层,所述第二涂层为外涂层,其中第二涂层包括颗粒状淀粉和流变改性剂,其中对于每100重量份淀粉颗粒,所述第二涂层含有的矿物或合成颜料低于20重量份,其中颗粒状淀粉具有5至100μm的平均粒径。
20.根据权利要求19的纸,其中对于每100重量份淀粉颗粒,所述第二涂层含有的矿物或合成颜料低于10重量份。
21.根据权利要求19的纸,其中对于每100重量份淀粉颗粒,所述第二涂层含有的矿物或合成颜料低于5重量份。
22.根据权利要求19的纸,所述第二涂层不含所述颜料。
23.根据权利要求19的纸,其中颗粒状淀粉具有10至80μm的平均粒径。
24.根据权利要求23的纸,其中颗粒状淀粉具有15至60μm的平均粒径。
25.根据权利要求24的纸,其中颗粒状淀粉具有20至50μm的平均粒径。
26.根据权利要求25的纸,其中淀粉来源于土豆、木薯、小麦、玉米或燕麦。
27.根据权利要求25的纸,其中淀粉来源于蜡质玉米。
28.根据权利要求26的纸,其中淀粉来源于土豆或小麦。
29.根据权利要求19-28中任一项的纸在平版印刷中的用途。
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GB1499235A (en) * | 1975-02-14 | 1978-01-25 | Polysar Ltd | Coating of paper using a composition comprising a latex of a rubbery film-forming polymer and ungelatinized starch granules |
EP0770493A1 (en) * | 1995-10-24 | 1997-05-02 | Oji Paper Co., Ltd. | Support and ink jet recording material containing the same |
CN1318667A (zh) * | 2000-04-12 | 2001-10-24 | 罗姆和哈斯公司 | 具有改善印刷质量的纸张及其制备方法 |
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EP2024563A1 (en) | 2009-02-18 |
EP2024563B8 (en) | 2013-09-25 |
CN101460679A (zh) | 2009-06-17 |
WO2007140992A1 (en) | 2007-12-13 |
US8129033B2 (en) | 2012-03-06 |
US20100015459A1 (en) | 2010-01-21 |
EP2024563B1 (en) | 2013-08-14 |
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